WO2014018122A1 - Method of forming a light emitting diode module - Google Patents
Method of forming a light emitting diode module Download PDFInfo
- Publication number
- WO2014018122A1 WO2014018122A1 PCT/US2013/033103 US2013033103W WO2014018122A1 WO 2014018122 A1 WO2014018122 A1 WO 2014018122A1 US 2013033103 W US2013033103 W US 2013033103W WO 2014018122 A1 WO2014018122 A1 WO 2014018122A1
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- WO
- WIPO (PCT)
- Prior art keywords
- refractive index
- transparent semiconductor
- polymer layer
- cgc
- thickness
- Prior art date
Links
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/36—Carbonitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/44—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0025—Processes relating to coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Definitions
- the disclosure relates to a method of forming a light emitting diode module that includes a compositional graded coating comprising a gradient including SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) along the thickness.
- LEDs light emitting diodes
- LEDs produce light by a process of electroluminescence, generally include one or more diodes that emit light when activated, and typically utilize either flip chips or wire-bonded chips that are connected to diodes to provide power.
- Many electronic articles also include tie layers, optical layers, substrates, superstrates, and/or additional materials to provide protection from environmental factors.
- LED efficiency is related to an amount of useful light produced and emitted based on a certain electrical input.
- Uncoated optoelectronic semiconductors tend to exhibit a high refractive index relative to open air which impedes passages of photons at sharp angles relative to the surface of the optoelectronic semiconductor that contacts the air. This property affects the light transmission efficiency of the LEDs.
- the transmission of useful light can be limited by optical interference, Fresnel and total internal reflection, and absorption of the light by the optical layers, tie layers, substrates, and superstrates, in addition to other factors.
- the critical angle 0 C is the angle of light incidence above which total internal reflection occurs - the light is completely reflected back by the boundary (interface).
- the larger the critical angel 0 C the more light will escape the LED.
- One method of increasing the 0 C is by increasing the refractive index of the surrounding medium, Since the light exiting the LED tends to be wide-angle distributed, antireflective coatings can be used but usually need to be efficient over a broad range of angles of light incidence.
- single-layer antireflective coatings provide minimum reflection at a specific wavelength and angle and tend to only be effective for small ranges of angles of incident light.
- conventional antireflective coatings that include silicon oxide and nitride are prone to formation of defects at various interfaces because of high temperatures or plasma powers required for deposition. Accordingly, there remain opportunities for improvement.
- This disclosure provides a light emitting diode module that includes a transparent semiconductor having a refractive index of 2.7 + 1.2, a polymer layer disposed on the transparent semiconductor and having a refractive index of 1.5 + 0.2, and a compositional graded coating (CGC) disposed on the transparent semiconductor and sandwiched between the transparent semiconductor and the polymer layer.
- the CGC has a thickness and a refractive index varying along the thickness from a first refractive index from (2.2 + 0.5 to 3.3 + 0.4) at a first end to a second refractive index of 1.5 + 0.2 at a second end adjacent to the polymer layer.
- the CGC also includes a gradient including SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) along the thickness.
- This disclosure also provides a method of forming the module wherein the method includes continuously depositing the CGC on the transparent semiconductor using chemical vapor deposition, and subsequently disposing the polymer layer on the CGC.
- Figure 1A is a side view of one embodiment of the module of this disclosure including a polymer layer disposed on, and spaced apart from, a transparent semiconductor, and a compositional graded coating disposed on, and in direct contact with, the transparent semiconductor, and sandwiched between the transparent semiconductor and the polymer layer.
- Figure IB is a side view of one embodiment of the module of this disclosure including a polymer layer disposed on, and spaced apart from, an LED as a transparent semiconductor, and a compositional graded coating disposed on, and in direct contact with, the LED, and sandwiched between the LED and the polymer layer.
- Figure 2 is an FT-IR spectrum of SiC:H and SiOCN:H films with varying contents of nitrogen and oxygen.
- Figure 3A is an XPS compositional profile of elemental concentration as a function of thickness of a compositional graded coating of this disclosure formed using (CFL ⁇ SiH as a source of Si-C.
- Figure 3B is an XPS compositional profile of elemental concentration as a function of thickness of a compositional graded coating of this disclosure formed using SiH 4 and C2H4 as sources of Si-C.
- Figure 4 is a line graph of refractive index, deposition rate, and absorption coefficient of coatings as functions of low frequency power in a dual-frequency PECVD reaction chamber using (CFL ⁇ SiH.
- Figure 5 is a line graph of refractive index, deposition rate, and absorption coefficient of coatings as functions of oxygen flow rate in a dual-frequency PECVD reaction chamber using (CFL ⁇ SiH.
- Figure 6 is a spectra of reflection as a function of wavelength of a bare Si substrate (BareSi), the same substrate including a polymer layer disposed thereon (SiEnc), a single layer antireflective coating with a polymer layer (ARC/Enc) , and two different CGCs of this disclosure including a polymer layer disposed thereon (CGClEnc and CGC2Enc).
- Figure 7 is a line graph of reflectance of a bare Si substrate (SiRef - R), the same Si substrate including a CGC (formed using (CH 3 ) 3 SiH) of this disclosure disposed thereon (CGC - R), the same Si substrate including the same CGC and the polymer layer (CGC.Enc - R), a glass reference transmittance (Glass Ref -T) and the same glass reference including a CGC of this disclosure (CGC - T).
- Figure 8 is a line graph of photoluminescent intensity (cps) as a function of wavelength of a CGC of this disclosure (formed using (CFL ⁇ SiH) with a three- component Gaussian model fit and a bare Si reference wafer.
- Figure 9 is a line graph of light reflection ( ) as a function of the wavelength of light of A1N disposed on a Si substrate, a first CGC of this disclosure (formed using (CH 3 ) 3 SiH) disposed on the AIN/Si, and a second based CGC of this disclosure (formed using (CH 3 ) 3 SiH) disposed on the AIN/Si.
- Figure 10 is a line graph of reflection as a function of the wavelength of light of A1N disposed on a Si substrate, a first CGC of this disclosure (formed using (CH 3 ) 3 SiH) disposed on the AIN/Si, and a second CGC of this disclosure (formed using (CH 3 ) 3 SiH) disposed on the AIN/Si.
- Figure 11A is a reflectance spectra of a A ⁇ C GaN reference, a first CGC of this disclosure (formed using (CF ⁇ SiH) disposed on the A ⁇ C GaN reference, a second CGC of this disclosure (formed using (CH 3 ) 3 SiH) disposed on the Al 2 C>3/GaN reference, and a third CGC of this disclosure (formed using SiH 4 ).
- Figure 1 IB is a transmittance spectra of a A ⁇ C GaN reference, a first CGC of this disclosure (formed using (CF ⁇ SiH) disposed on the A ⁇ C GaN reference, a second CGC of this disclosure (formed using (CF ⁇ SiH) disposed on the A ⁇ C GaN reference, and a third CGC of this disclosure (formed using SiH 4 ).
- Figure 12A is a reflectance spectra of a A ⁇ C GaN reference, a first CGC of this disclosure (formed using (CF ⁇ SiH) disposed on the A ⁇ C GaN reference, and a second CGC of this disclosure (formed using (CF ⁇ SiH) disposed on the A ⁇ C GaN reference and also including a polymer layer disposed on the second CGC.
- Figure 12B is a transmittance spectra of a A ⁇ C GaN reference, a first CGC of this disclosure (formed using (CF ⁇ SiH) disposed on the A ⁇ C GaN reference, and a second CGC of this disclosure (formed using (CF ⁇ SiH) disposed on the A ⁇ C GaN reference and also including a polymer layer disposed on the second CGC.
- Figure 13 A is a reflectance spectra of a Al 2 C>3/GaN reference, a first CGC of this disclosure (formed using SiH 4 ) disposed on the Al 2 C>3/GaN reference, and a second CGC of this disclosure (formed using SiH 4 ) disposed on the Al 2 C>3/GaN reference and also including a polymer layer disposed on the second CGC.
- Figure 13B is a transmittance spectra of a Al 2 C>3/GaN reference, a first CGC of this disclosure (formed using SiH 4 ) disposed on the Al 2 C>3/GaN reference, and a second CGC of this disclosure (formed using SiH 4 ) disposed on the Al 2 C>3/GaN reference and also including a polymer layer disposed on the second CGC.
- Figure 14 is a graph of refractive index of a compositional graded coating disposed on GaN as a function of thickness including a third order exponential model fit.
- Figure 15 is an example of a 2-dimensional gradient.
- This disclosure provides a light emitting diode (LED) module and a method of forming the module.
- the module tends to be a solid-state device that emits light in a spectral range when a forward bias is applied.
- the wavelength of the emitted light is typically dependent on the energy bandgap (E g ) of a transparent semiconductor used in the active region of the device.
- the transparent semiconductor includes a p-n junction with a multiple-quantum-well active region and carrier- confining layers.
- the module typically has a light reflection of less than 10, 7, 5, 4, 3, 2, or 1% over a range of wavelengths from about 300 to about 1700 nanometers.
- the light reflection is typically measured using a spectrophotometer and/or an ellipsometer such as a Cary 5000 UV-Vis-NIR spectrophotometer commercially available from Agilent Technologies Inc. (Santa Clara, California).
- the module may be alternatively described as a solid state light (e.g. a solid state light that includes an LED) or as solid state lighting and can be used in any application including, but not limited to, instrument panels & switches, courtesy lighting, turn and stop signals, household appliances, VCR/DVD/ stereo/audio/video devices, toys/games instrumentation, security equipment, switches, architectural lighting, signage (channel letters), machine vision, retail displays, emergency lighting, neon and bulb replacement, flashlights, accent lighting full color video, monochrome message boards, in traffic, rail, and aviation applications, in mobile phones, PDAs, digital cameras, lap tops, in medical instrumentation, bar code readers, color & money sensors, encoders, optical switches, fiber optic communication, and combinations thereof.
- a solid state light e.g. a solid state light that includes an LED
- solid state lighting e.g. a solid state light that includes an LED
- solid state lighting e.g. a solid state light that includes an LED
- solid state lighting e.g. a solid state
- the module includes a transparent semiconductor.
- the transparent semiconductor is not particularly limited and may be further described as one or more of semiconductor LEDs, organic LEDs, polymer LEDs, quantum dot LEDs, infrared LEDs, visible light LEDs (including colored and white light), ultraviolet LEDs, and combinations thereof.
- the transparent semiconductor may include a single layer or multiple layers.
- the transparent semiconductor is typically at least 75, 80, 85, 90, 95, 96, 97, 98, or 99% transparent to the ultraviolet (UV), visible and/or infrared (IR) light typically measured using a spectrophotometer and/or an ellipsometer.
- the transparent semiconductor may alternatively include or be further defined as AI2O 3 , SiC, a semiconductor chosen from Group III and/or Group IV from the periodic table, and/or combinations thereof.
- the transparent semiconductor is chosen from GaN, AlGaN, A1N, GaAs, AlGaAs, InP, InGaAsP, and combinations thereof.
- the transparent semiconductor has a refractive index of (about) 1.5 to 3.9, i.e., 2.7 + 1.2, 1.1, 1, 0.75, 0.5, 0.25, or 0.1.
- the transparent semiconductor has a thickness from 0.2 to 2.0, from 0.4 to 1.8, from 0.6 to 1.6, from 0.8 to 1.4, or from 1.0 to 1.2, mm.
- the module may also include one or more layers or components known in the art as typically associated such modules.
- the module may include one or more drivers, optics, heat sinks, housings, lenses, power supplies, fixtures, wires, electrodes, circuits, and the like.
- the module may include two, three, or multiple (layers of) transparent semiconductors, each of which may independently be the same or different from those described above. Typically, several layers of transparent semiconductors are utilized to form an LED.
- a top (e.g. outermost) transparent semiconductor, of the multiple layers is further defined as a light emitting diode.
- a top layer of multiple layers of the transparent semiconductor may be further defined as a light emitting diode.
- the module may include a phosphor.
- the phosphor is not particularly limited and may include any known in the art.
- the phosphor is made from a host material and an activator, such as copper-activated zinc sulfide and silver- activated zinc sulfide.
- Suitable but non-limiting host materials include oxides, nitrides and oxynitrides, sulfides, selenides, halides or silicates of zinc, cadmium, manganese, aluminum, silicon, or various rare earth metals.
- Additional suitable phosphors include, but are not limited to, Zn 2 SiC>4:Mn (Willemite); ZnS:Ag+(Zn,Cd)S:Ag; ZnS:Ag+ZnS:Cu+Y 2 0 2 S:Eu; ZnO:Zn; KC1; ZnS:Ag,Cl or ZnS:Zn; (KF,MgF 2 ):Mn; (Zn,Cd)S:Ag or (Zn,Cd)S:Cu; Y 2 0 2 S:Eu+Fe 2 03, ZnS:Cu,Al; ZnS:Ag+Co-on-Al 2 0 3 ;(KF,MgF 2 ):Mn;
- the phosphor may be present in any portion of the module.
- the phosphor may be present as a discrete layer in the module or as part of an independent composition.
- the phosphor may be present in an independent layer or may be combined with a composition, e.g. in a gradient pattern, homogeneously dispersed throughout, or present in higher concentrations in some areas of the composition and in lower concentration in other areas of the composition.
- the phosphor is present in a lens of the module.
- the module may also include a release liner.
- the release liner may be any known in the art such as siliconized PET or a fluorinated liner. These release liners are typically smooth but can also be textured e.g. in or as an anti-reflective surface.
- the module also includes a polymer layer that is disposed on the transparent semiconductor and that has a refractive index of 1.3 to 1.8, i.e., 1.5 + 0.05, 0.1, 0.15, 0.2, or + 0.2, or 0.3, as determined using a spectroscopic ellipsometer refractometer.
- the refractive index of the polymer layer is approximately matched to the refractive index of the compositional graded coating, e.g. ⁇ 0.1, described in greater detail below.
- the polymer layer also typically has a light transparency of at least 85, 90, 95, 96, 97, 98, 99, or 99.5, percent, as determined using a spectrophotometer.
- the polymer layer has a light transparency of about 100 percent (- 10, 5, 2, 1, 0.75, 0.5, 0.25 ).
- the terminology "disposed on” includes the polymer layer disposed on and in direct contact with the transparent semiconductor or on and spaced apart from the transparent semiconductor yet still disposed thereon, as set forth in Figure 1. Typically, the polymer layer is disposed on and spaced apart from the transparent semiconductor.
- the polymer layer may have a thickness of at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, or 125, ⁇ .
- the polymer layer may have a thickness from 50 to 150, from 60 to 140, from 70 to 130, from 80 to 120, from 90 to 110, from 50 to 250, from 60 to 350, from 70 to 450, from 80 to 550, or from 100 to 1000, ⁇ .
- the polymer layer has a thickness of about 300 ⁇ .
- the polymer layer has a thickness that is about the same or longer than the coherence length of emitted light, whether visible light, UV light, and IR light. This thickness minimizes interference effects due to an optical path length greater than the coherence length of emitted light. If the polymer layer is overly thinned, increased interference may occur which may cause coloring and/or spectral effects.
- the polymer layer may be formed from and/or include an inorganic compound, and organic compound, or a mixture of organic and inorganic compounds. These compounds may or may not require curing.
- the polymer layer may be formed from and/or include metals, polymers, plastics, silicones, glass, sapphire, and the like so long as the refractive index is as described above.
- the polymer layer is ethylene vinyl acetate (EVA), glass, a silicone, and/or an acrylate.
- EVA ethylene vinyl acetate
- the polymer layer is transparent to light as determined using a spectrophotometer.
- the polymer layer may be formed from a curable composition including silicon atoms.
- the curable composition includes a hydrosilylation curable polydimethylsiloxane (PDMS).
- PDMS hydrosilylation curable polydimethylsiloxane
- the polymer layer may be as described in one or more of PCT/US09/01623, PCT/US09/01621, and/or PCT/US09/62513, each of which is expressly incorporated herein by reference.
- the polymer layer may be an inner layer or an outermost layer of the module.
- the module may include multiple polymer layers, i.e., a second and optionally a third polymer layer, or more. Any additional polymer layer may be the same or different from the polymer layer described above.
- the module includes the polymer layer described above and a second polymer layer. Further, the polymer layer may be transparent to UV and/or visible light and the second (or additional) polymer layers may be transparent to UV and/or visible light.
- the module also includes a compositional graded coating (CGC) that is disposed on the transparent semiconductor and sandwiched between the transparent semiconductor and the polymer layer, as set forth in Figure 1.
- CGC compositional graded coating
- disposed on describes the CGC disposed on and in direct contact with the transparent semiconductor. This terminology also describes the CGC spaced apart from the transparent semiconductor, yet still disposed thereon.
- the module may include two or more CGCs that may be the same or different from one another and each of which may be disposed in any location in the module.
- the CGC has a thickness which is typically from 50 to 1000, from 50 to 950, from 100 to 900, from 150 to 850, from 200 to 800, from 250 to 750, from 300 to 700, from 350 to 650, from 400 to 600, from 450 to 550, from 50 to 750, from 100 to 500, from 150 to 450, from 200 to 300, from 250 to 450, from 350 to 450, about 400, about 450, or about 500, nm.
- the CGC has a thickness from 50 to 400 nanometers which is typically chosen to reduce light absorption.
- the CGC has a thickness from 60 to 390, from 70 to 380, from 80 to 370, from 90 to 360, from 100 to 350, from 110 to 340, from 120 to 330, from 120 to 320, from 130 to 310, from 140 to 300, from 150 to 290, from 160 to 280, from 170 to 270, from 180 to 260, from 190 to 250, from 200 to 240, or from 210 to 230, nm.
- the CGC has a thickness and a refractive index varying along the thickness from a first refractive index from (1.7 to 3.9, i.e., 2.2 + 0.5 to 3.3 + 0.4) at a first end to a second refractive index of 1.3 to 1.7, i.e., 1.5 + 0.2, at a second end adjacent to the polymer layer.
- the first refractive index may be alternatively described as from 2.25 to 3.15, from 2.3 to 3.1, from 2.35 to 3.15, from 2.4 to 3.1, from 2.45 to 3.05, from 2.5 to 3, from 2.55 to 2.95, from 2.6 to 2.9, from 2.65 to 2.85, from 2.7 to 2.8, or from 2.75 to 2.8, each + 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, or 0.05.
- the second refractive index may be alternatively described as 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1.
- the first end may be further defined as an interface between the CGC and the transparent semiconductor.
- the first end may be further defined as an interface between the CGC and an intermediate layer, which is described in greater detail below.
- the second end may be further defined as an interface between the CGC and the polymer layer.
- the refractive index of the CGC at a particular point along the thickness is typically determined by instantaneous deposition conditions. This refractive index corresponds to the refractive index of a homogeneous coating deposited using identical, but static, deposition conditions for the full coating thickness.
- the CGC includes a gradient of the refractive indices described above.
- the CGC includes a gradient of SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) along the thickness, e.g. with varying hydrogen content and/or Si to C and/or O to Si compositional ratios.
- the CGC includes a gradient of refractive indices and/or a gradient of SiC:H and SiOCN:H; SiC:H and SiOC:H; or SiC:H and Si:H.
- the CGC includes a gradient of refractive indices and/or a gradient of Si:H, SiC:H, SiOCN:H, and SiOC:H.
- the CGC includes a gradient of a carbide and an oxycarbide along the thickness.
- carbide is further defined as hydrogenated silicon carbide (SiC:H) and the oxycarbide is further defined as hydrogenated silicon oxycarbide (SiOC:H).
- the gradient in whole or in part, can proceed from SiC:H to SiOCN:H, from SiC:H to SiOC:H, from SiC:H to Si:H, from SiOCN:H to SiOC:H, from SiOCN:H to Si:H, from SiOC:H to Si:H, from Si:H to SiOC:H, from Si:H to SiOCN:H, from Si:H to SiC:H, any reverse order thereof, or any combination thereof.
- the CGC includes both a gradient of the refractive indices and of the amounts of SiC:H and (SiOCN:H; SiOC:H; and/or Si:H).
- the gradients of the refractive indices and of the amounts of SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) may independently be continuous (e.g. uninterrupted and/or consistently changing) or stepped, e.g. discontinuous or changing in one or more steps.
- the terminology "gradient” typically describes a graded change in the magnitude of the refractive indices and/or the amounts of SiC:H and (SiOCN:H; SiOC:H; and/or Si:H), e.g.
- the gradient may be further defined as a vector field which points in the direction of the greatest rate of increase and whose magnitude is the greatest rate of change.
- the gradient may be further defined as a series of 2 dimensional vectors at points on the CGC with components given by the derivatives in horizontal and vertical directions. At each point on the CGC, the vector points in the direction of largest possible intensity increase, and the length of the vector corresponds to the rate of change in that direction.
- An example of a 2-dimensional gradient is set forth in Figure 15.
- the CGC has a continuous gradient with one extreme of the gradient selected to approximately match the refractive index of the transparent semiconductor or the intermediate layer, described in greater detail below.
- the index of refraction of the CGC smoothly shifts from approximately matching (e.g. + 0.2) the refractive index of the intermediate layer to a refractive index that approximately matches (e.g. + 0.2) that of the polymer layer to avoid or minimize significant discontinuity in optical characteristics at interfaces therebetween.
- the CGC includes hydrogenated silicon (Si:H) at the interface with the transparent semiconductor and then the continuous gradient gradually changes to hydrogenated silicon carbide (SiC:H) and then to hydrogenated silicon oxycarbonitride (SiOCN:H) near the interface with the polymer layer.
- the CGC may include hydrogenated silicon carbide (SiC:H) (e.g. at an interface with the transparent semiconductor) and then gradually change to hydrogenated silicon oxycarbonitride (SiOCN:H) near the interface with the polymer layer.
- the module includes the intermediate layer including the Si:H, as described in greater detail below.
- the hydrogenated silicon carbide (SiC:H) is typically present near the interface with the intermediate layer (e.g. the Si:H).
- Changing the composition and/or density of the CGC along with grading the optical impedance of the CGC may provide a smooth transition between the transparent semiconductor and the polymer layer approximately matching the optical parameters (e.g. + 0.2) of each at the relevant interfaces.
- the CGC may have a variety of physical properties that benefit performance of the module.
- the CGC emits light having a wavelength from 375 to 675, from 400 to 650, from 425 to 625, from 450 to 600, from 475 to 575, from 500 to 550, from 525 to 550, from 450 to 700, or from 500 to 600, nm, when excited with light having a wavelength from 300 to 450, from 300 to 400, from 310 to 390, from 320 to 380, from 330 to 370, from 340 to 360, or from 340 to 350, nm.
- the module may also include Si:H disposed between the polymer layer and the transparent semiconductor.
- the Si:H may be included in the intermediate layer disposed between the CGC and the transparent semiconductor.
- the intermediate layer may have a refractive index from 3 to 3.3 + 0.2 or from 3 to 3.5 + 0.2.
- the CGC has a refractive index varying along the thickness from the first refractive index of 2.2 + 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, or 0.05 at the first end to the second refractive index of 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1 at the second end adjacent to the polymer layer.
- the Si:H may be present in the CGC such that the gradient includes Si:H, SiC:H and optionally SiOC:H and/or SiOCN:H.
- the CGC has a refractive index varying along the thickness from the first refractive index of 3.3 + 0.5, 0.4, 0.3, 0.2, or 0.1 at the first end to the second refractive index of 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1 at the second end adjacent to the polymer layer.
- the Si:H may also be present both in the gradient and in the intermediate layer.
- the module may also include the intermediate layer, e.g. an inorganic layer.
- the intermediate layer is disposed on the transparent semiconductor and sandwiched between the transparent semiconductor and the CGC.
- the terminology "disposed on” includes the intermediate layer disposed on and in direct contact with the transparent semiconductor. This terminology also includes the intermediate layer spaced apart from the transparent semiconductor yet still disposed thereon.
- the intermediate layer is not particularly limited and may include any inorganic (i.e., non-organic) element or compound known in the art.
- the intermediate layer may include a content of organic compounds in addition to inorganic compounds.
- the intermediate layer includes silicon carbide.
- the intermediate layer includes Si:H.
- the intermediate layer may be used to compatibilize the CGC and the transparent semiconductor.
- the intermediate layer may have a refractive index within 1, 2, 3, 4, 5, 10, 15, 20, or 25 percent to that of the CGC and/or to that of the transparent semiconductor.
- the intermediate layer may have a refractive index from 3 to 3.3 + 0.2 or from 3 to 3.5 + 0.2.
- the CGC has a refractive index varying along the thickness from the first refractive index of 2.2 + 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, or 0.05 at the first end to the second refractive index of 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1 at the second end adjacent to the polymer layer.
- the Si:H may be present in the compositional graded coating such that the gradient includes Si:H, SiC:H and SiOCN:H.
- the CGC has a refractive index varying along the thickness from the first refractive index of 3.3 + 0.5, 0.4, 0.3, 0.2, or 0.1 at the first end to the second refractive index of 1.45 ⁇ 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1 at the second end adjacent to the polymer layer.
- the Si:H may also be present both in the gradient and in the intermediate layer.
- the module may also include a superstrate and/or substrate which may independently include any material known in the art.
- the superstrate may be utilized with the polymer layer.
- the substrate provides protection to a rear surface of the module and the superstrate provides protection to a front surface of the module.
- the substrate and/or superstrate may each be soft and flexible or rigid and stiff.
- the substrate and/or superstrate may include rigid and stiff segments while simultaneously including soft and flexible segments.
- the substrate may be transparent to light, may be opaque, or may not transmit light. Most typically, the superstrate allows at least some light to penetrate the module.
- the substrate and/or superstrate may include glass, stainless steel, metal foils, polyimides, ethylene-vinyl acetate copolymers, and/or organic fluoropolymers such as ethylene tetrafluoroethylene (ETFE), Tedlar ® (polyvinylfluoride, available from DuPont), polyester/Tedlar ® , Tedlar ® /polyester/Tedlar ® , polyethylene terephthalate (PET) alone or coated with silicon and oxygen based materials (SiO x ), and combinations thereof.
- the substrate is selected from the group of polyvinylfluoride and polyethylene.
- the substrate may alternatively be a PET/SiO x -PET/Al substrate, wherein x is a number having a value from 1 to 4.
- the substrate and/or superstrate may include silicone, may consist essentially of silicone and not include, or include less than 1 wt , organic monomers or organic polymers, or may consist of silicone.
- the optional silicone chemistry of the substrate and/or superstate may include any type known in the art.
- the substrate and/or superstate may be load bearing or non-load bearing. Typically, the substrate is load bearing and the superstate is not load bearing.
- the substrate is typically a bottom and outermost layer of the module. Bottom layers are typically positioned behind the transparent semiconductor and serve as mechanical support.
- the superstrate is typically a top and outermost layer of the module and may be oriented towards the light source. If both a substrate and superstrate are utilized, the substrate and superstrate each typically act as outermost layers and sandwich all other components of the module therebetween.
- the module may be free of a “backsheet” and/or "front glass.”
- backsheet typically describes a substrate, as described above.
- the backsheet includes metal foils, polyimides, ethylene-vinyl acetate copolymers, and/or organic fluoropolymers such as ethylene tetrafluoroethylene (ETFE), Tedlar ® (polyvinylfluoride), polyester/Tedlar ® , Tedlar ® /polyester/Tedlar ® , polyethylene terephthalate (PET) alone or coated with silicon and oxygen based materials (SiOx), and combinations thereof.
- ETFE ethylene tetrafluoroethylene
- Tedlar ® polyvinylfluoride
- polyester/Tedlar ® polyester/Tedlar ®
- Tedlar ® /polyester/Tedlar ® polyethylene terephthalate
- SiOx silicon and oxygen based materials
- the “backsheet” may alternatively be the PET/SiO x -PET/Al substrate.
- the module may be free of the “backsheet” and still include one or more compounds or components described above as a substrate.
- the module may still include a substrate and be free of a "backsheet.”
- the terminology “front glass” typically describes used as a superstrate that allows light to pass through.
- the module may be free of the "front glass” and still include one or more compounds or components described above as a superstrate.
- the module may still include a superstrate and be free of "front glass.”
- the module may also include one or more tie layers which may bind one or more other layers to each other.
- the one or more tie layers may be disposed on the substrate to bind the transparent semiconductor to the substrate and/or one or more other layers.
- the module includes multiple tie layers, e.g. first, second, and/or a third tie layer. Any second, third, or additional tie layer may be the same or different from the (first) tie layer. Thus, any second, third or additional tie layer may be formed from the same material or from a different material than the (first) tie layer.
- the second tie layer may be disposed on the (first) tie layer and/or may be disposed on the transparent semiconductor.
- the one or more tie layers are each typically transparent to UV and/or visible light. In one embodiment, the tie layer has high transmission across visible wavelengths, long term stability to UV and provides long term protection to the transparent semiconductor.
- the tie layers typically have a thickness from 1 to 50, more typically from 3 to 30, and most typically from 4 to 15, mils.
- the tie layers have a thickness from 1 to 30, from 1 to 25, from 1 to 20, from 3 to 17, from 5 to 10, from 5 to 25, from 10 to 15, from 10 to 17, from 12 to 15, from 10 to 30, or from 5 to 20, mils.
- the tie layer(s) may be as described in PCT/US09/01623, PCT/US09/01621, and/or PCT/US09/62513, each of which is expressly incorporated herein by reference.
- the method of forming the module includes continuously depositing the CGC on the transparent semiconductor using chemical vapor deposition (CVD) and subsequently disposing the polymer layer on the CGC to form the module.
- the step of continuously depositing the CGC may be accomplished using plasma-enhanced chemical vapor deposition (PECVD), e.g., in a reactive ion-etching configuration, dual frequency configuration, electron cyclotron resonance configuration or inductively-coupled plasma mode. Any type of CVD known in the art may be utilized.
- PECVD plasma-enhanced chemical vapor deposition
- the terminology "continuously depositing” typically describes the CVD operating without interruption or with few interruptions.
- the continuous operation of the CVD minimizes or eliminates formation of additional optical interfaces in the CGC which allows a gradient to be formed with minimized reflection, absorption, and interference and also allows the module to be formed with increased durability and flexibility and optimized optical properties.
- the step of continuously depositing may occur below room temperature, at room temperature (referred to herein as "RT” and is about 21 to 25°C), or above RT. In various embodiments, the temperature is about 50, 100, 200, 300, or 400, °C.
- a CVD system such as a PECVD system that mixes precursor gasses in vacuum chambers and excites mixtures of the gases with radio frequency (RF) generators attached to electrodes to create plasmas of ionized gasses.
- RF radio frequency
- Vacuum pressure, electrode power, temperature, and gas flow can be customized, see, e.g. the Figures.
- the PECVD system includes a powered parallel- plate electrode reactor with electrodes powered with two generators.
- One generator is typically a standard RF generator (also called a high frequency power supply (e.g.
- the PECVD system may also include a third electrode, for example chamber walls.
- the CVD system may operate in a dual frequency configuration (e.g. mode). Operation in the dual frequency configuration typically includes the operation of PECVD at a first and a second frequency simultaneously.
- the first frequency is typically between 50 and 400 kHz and can range from 60 to 390, from 70 to 380, from 80 to 370, from 90 to 360, from 100 to 350, from 110 to 340, from 120 to 330, from 130 to 320, from 140 to 310, from 150 to 300, from 200 to 290, from 210 to 280, from 220 to 270, from 230 to 260, or from 240 to 250, KHz.
- the first frequency ranges between 70 and 400 KHz. In another embodiment, the first frequency is about 380 KHz.
- the second frequency is typically between 10 MHz and 1, or more than 1, GHz. In various embodiments, the second frequency ranges from 10 to 50, from 10 to 40, from 12 to 30, from 13 to 20, from 13 to 15, or from 13 to 14, MHz. In one embodiment, the second frequency is about 13.56 MHz.
- the power of the electrodes used in the CVD system can be varied. In various embodiments, two electrodes are utilized wherein the power to each electrode may be varied independently.
- the power to a first electrode typically ranges from 10 to 1000, from 10 to 600, from 50 to 200, from 80 to 160, from 90 to 150, from 100 to 140, from 110 to 130, or about 120, Watts.
- the first electrode is typically associated with the first frequency described above.
- the power to a second electrode typically ranges from 10 to 1000, from 10 to 600, from 200 to 400, from 210 to 390, from 220 to 380, from 230 to 370, from 240 to 360, from 250 to 350, from 260 to 340, from 270 to 330, from 280 to 320, from 290 to 310, or about 300, Watts.
- the second electrode is typically associated with the second frequency described above.
- the second (e.g. high) frequency may influence plasma density due to more efficient displacement current and sheath heating mechanisms.
- the first (e.g. low) frequency may influence peak ion bombardment energy. Accordingly, separate adjustment and customization of ion bombardment energy and plasma density may be utilized to influence control of deposition stress and optical properties. In addition, greater control of lattice spacing of the CGC as well as stacking faults in crystal structure, control of pin holes and location of interstitial atoms, and minimization of deposition tension and stress may be customized.
- the step of continuously depositing the CGC may include one or more sub- steps.
- the step of continuously depositing includes introducing a source of silicon, such as monosilane (SiH 4 ) or (CH 3 ) 3 SiH), to the transparent semiconductor, introducing a hydrocarbon gas (e.g. methane, ethylene, acetylene, or any known in the art) to the transparent semiconductor, and introducing at least one of nitrous oxide, oxygen, and carbon dioxide to the transparent semiconductor.
- a source of silicon such as monosilane (SiH 4 ) or (CH 3 ) 3 SiH
- a hydrocarbon gas e.g. methane, ethylene, acetylene, or any known in the art
- the step of introducing "to the transparent semiconductor” may be alternatively defined as introducing "into the plasma” or "into a CVD chamber” wherein the transparent semiconductor is exposed to the plasma and/or the source of the silicon, the hydrocarbon gas, or the other gases, in the CVD chamber.
- the introduction of the source of silicon allows the CVD process to produce the Si:H of the module and/or gradient.
- the introduction of the hydrocarbon gas allows the CVD process to produce the SiC:H of the gradient.
- the introduction of at least one of the nitrous oxide, oxygen, and carbon dioxide allows the CVD process to produce the SiOCN:H of the gradient.
- the method may alternatively include the step of introducing a source of nitrogen (e.g. nitrous oxide) and/or the step of introducing a source of oxygen (e.g. nitrous oxide and/or oxygen), to the transparent semiconductor (e.g. into the plasma).
- the source of silicon is introduced at a high power (e.g. above 300 Watts).
- This step typically forms a first portion of the gradient with a high refractive index (e.g. ⁇ 2.7 to 3.6).
- the method includes the step of increasing pressure (e.g. increasing from 50 to 500 mTorr). Typically, increasing the pressure decreases the refractive index of the gradient that is being formed.
- the method includes the step of decreasing power and increasing pressure to continue to form the CGC.
- the total gas flow can range from 200 to 3,000, from 400 to 2,000, or from 450 to 850, standard cubic centimeters per minutes (seem).
- the temperature can range from 20 to 400, from 30 to 250, or from 30 to 80°C.
- the pressure can range from 20 to 2000, from 20 to 1000, from 80 to 800, from 50 to 500, or from 90 to 200, mTorr.
- the method also includes the step of disposing the polymer layer on the CGC.
- the step of disposing the polymer layer may be further defined as disposing a curable composition on the CGC and then either partially or completely curing the curable composition to form the polymer layer.
- the polymer layer may be disposed on the CGC without any additional curing.
- the polymer layer and/or curable composition may be applied using any suitable application (dispensing) method known in the art including spray coating, flow coating, curtain coating, dip coating, extrusion coating, knife coating, screen coating, laminating, melting, pouring, and combinations thereof.
- the polymer layer is formed from a liquid and the step of disposing the polymer layer is further defined as disposing a liquid on the CGC and curing the liquid on the CGC to form the polymer layer.
- the curable composition is supplied to a user as a multi-part system, e.g. including first and second parts. The first and second parts may be mixed immediately prior to use. Alternatively, each component and/or a mixture of components may be applied individually.
- the polymer layer is formed from the curable composition and the method further includes the step of partially curing, e.g. "pre-curing," the curable composition to form the polymer layer.
- the method further includes the steps of applying the curable composition to the CGC and curing the curable composition to form the polymer layer.
- the curable composition is cured prior to the step of disposing the polymer layer on the substrate.
- the curable composition may be cured at any temperature, e.g. from 25 to 200 °C.
- the curable composition may also be cured for any time, e.g. from 1 to 600 seconds. Alternatively, the curable composition may be cured in a time of greater than 600 seconds, as determined by one of skill in the art.
- curable silicone compositions include hydrosilylation- curable silicone compositions, condensation-curable silicone compositions, radiation- curable silicone compositions, and peroxide-curable silicone compositions.
- a hydrosilylation-curable silicone composition typically includes an organopolysiloxane having an average of at least two silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms per molecule; an organosilicon compound in an amount sufficient to cure the organopolysiloxane, wherein the organosilicon compound has an average of at least two silicon-bonded hydrogen atoms or silicon- bonded alkenyl groups per molecule capable of reacting with the silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the organopolysiloxane; and a catalytic amount of a hydrosilylation catalyst.
- a condensation-curable silicone composition typically includes an organopolysiloxane having an average of at least two silicon-bonded hydrogen atoms, hydroxy groups, or hydrolysable groups per molecule and, optionally, a cross-linking agent having silicon-bonded hydrolysable groups and/or a condensation catalyst.
- a radiation-curable silicone composition typically includes an organopolysiloxane having an average of at least two silicon-bonded radiation- sensitive groups per molecule and, optionally, a cationic or free -radical photoinitiator depending on the nature of the radiation-sensitive groups in the organopolysiloxane.
- a peroxide-curable silicone composition typically includes an organopolysiloxane having silicon-bonded unsaturated aliphatic hydrocarbon groups and an organic peroxide.
- the silicone composition can be cured by exposing the composition to ambient temperature, elevated temperature, moisture, or radiation, depending on the type of curable silicone composition.
- the silicone composition can be cured by exposing the composition to a temperature from RT to 250 °C, alternatively from RT to 150 °C, alternatively from RT to 115 °C, at atmospheric pressure.
- the silicone composition is generally heated for a length of time sufficient to cure (cross-link) the organopolysiloxane.
- the film is typically heated at a temperature from 100 to 150 °C for a time from 0.1 to 3 h.
- the conditions for curing the composition depend on the nature of the silicon-bonded groups in the organopolysiloxane.
- the composition can be cured (i.e., cross-linked) by heating the composition.
- the composition can typically be cured by heating it at a temperature from 50 to 250 °C, for a period from 1 to 50 h.
- the condensation-curable silicone composition includes a condensation catalyst, the composition can typically be cured at a lower temperature, e.g., from RT to 150 °C.
- the curable silicone composition is a condensation-curable silicone composition including an organopolysiloxane having silicon-bonded hydrogen atoms
- the composition can be cured by exposing the composition to moisture or oxygen at a temperature from 100 to 450 °C for a period from 0.1 to 20 h.
- the condensation-curable silicone composition contains a condensation catalyst
- the composition can typically be cured at a lower temperature, e.g., from RT to 400°C.
- the curable silicone composition is a condensation-curable silicone composition including an organopolysiloxane having silicon-bonded hydrolysable groups
- the composition can be cured by exposing the composition to moisture at a temperature from RT to 250°C, alternatively from 100 to 200°C, for a period from 1 to 100 h.
- the silicone composition can typically be cured by exposing it to a relative humidity of 30% at a temperature from RT to 150 °C, for a period from 0.5 to 72 h. Cure can be accelerated by application of heat, exposure to high humidity, and/or addition of a condensation catalyst to the composition.
- the composition can be cured by exposing the composition to an electron beam.
- the accelerating voltage is from about 0.1 to 100 keV
- the vacuum is from about 10 to 10 ⁇ 3 Pa
- the electron current is from about 0.0001 to 1 ampere
- the power varies from about 0.1 watt to 1 kilowatt.
- the dose is typically from about 100 microcoulomb/cm ⁇ to 100 coulomb/cm ⁇ , alternatively from about 1 to 10 coulombs/cm ⁇ .
- the time of exposure is typically from about 10 seconds to 1 hour.
- the radiation-curable silicone composition when the radiation-curable silicone composition further includes a cationic or free radical photoinitiator, the composition can be cured by exposing it to radiation having a wavelength from 150 to 800 nm, alternatively from 200 to 400 nm, at a dosage sufficient to cure (cross-link) the organopolysiloxane.
- the light source is typically a medium pressure mercury-arc lamp.
- the dose of radiation is typically from
- the silicone composition can be externally heated during or after exposure to radiation to enhance the rate and/or extent of cure.
- the curable silicone composition is a peroxide-curable silicone composition
- the composition can be cured by exposing it to a temperature from RT to 180 °C, for a period from 0.05 to 1 h.
- the method may also include the step(s) of disposing the transparent semiconductor on the polymer layer, the tie layer and/or the substrate.
- the transparent semiconductor may also include the CGC disposed thereon such that this step may be a part of, or a further definition of, the step of disposing the polymer layer on the CGC.
- the transparent semiconductor can be disposed (e.g. applied) by any suitable mechanisms known in the art but is typically applied using an applicator in a continuous mode. Other suitable mechanisms of application include applying a force to the transparent semiconductor to more completely contact the transparent semiconductor and the polymer layer, the CGC, the tie layer and/or the substrate, either directly or indirectly.
- the method includes the step of compressing the transparent semiconductor and the polymer layer, the CGC, the tie layer and/or the substrate. Compressing the transparent semiconductor and the polymer layer, the CGC, the tie layer and/or the substrate maximizes contact and maximize encapsulation, if desired.
- the step of compressing may be further defined as applying a vacuum to the transparent semiconductor and the polymer layer, the CGC, the tie layer and/or the substrate.
- a mechanical weight, press, or roller e.g. a pinch roller
- the step of compressing may be further defined as laminating.
- the method may include the step of applying heat to the module or any or all of the substrate, the CGC, the transparent semiconductor, polymer layer, and/or the tie layer. Heat may be applied in combination with any other step or may be applied in a discrete step.
- the entire method may be continuous or batch or may include a combination of continuous and batch steps.
- the step of disposing the polymer layer may be further defined as encapsulating at least part of the transparent semiconductor and/or the CGC with the polymer layer. More specifically, the polymer layer may partially or totally encapsulate the transparent semiconductor and/or CGC. Alternatively, the polymer layer may not encapsulate the transparent semiconductor and/or CGC. Partial encapsulation encourages more efficient manufacturing.
- the polymer layer allows for production of a module with the optical and chemical advantages of silicone. Additionally, use of silicone allows for formation of UV transparent tie layers and/or polymer layers and may increase cell efficiency by at least 1 to 5 relative . Use of peroxide catalysts, as described above, may also provide increased transparency and increased cure speeds. Sheets of the curable composition including silicone may be used for assembly of the module.
- the polymer layer and/or the tie layer may be further defined as a film and the step of disposing may be further defined as applying the film, e.g. applying the film to the CGC.
- the step of applying the film may be further defined as melting the film.
- the film may be laminated on the CGC.
- the method includes the step of laminating to melt the tie layer and/or the polymer layer.
- the method includes the step of applying the transparent semiconductor to a substrate by chemical vapor deposition. This step may be performed by any mechanisms known in the art.
- the method may also include the step of applying the additional tie layer, substrate, and/or superstrate.
- the module includes the transparent semiconductor, the polymer layer, and the CGC disposed on the transparent semiconductor and sandwiched between the transparent semiconductor and the polymer layer.
- the CGC relative to the module itself, may be formed by any method or process known in the art or the method described above.
- the CGC is formed using electrical heating, hot filament processes, UV irradiation, IR irradiation, microwave irradiation, X-ray irradiation, electronic beams, laser beams, plasma, RF, radio frequency plasma enhanced chemical vapor deposition (RF-PECVD), electron-cyclotron-resonance plasma-enhanced chemical vapor deposition (ECR-PECVD), inductively coupled plasma enhanced chemical vapor deposition (ICP-ECVD), plasma beam source plasma enhanced chemical vapor deposition (PBS- PECVD), and/or combinations thereof.
- RF-PECVD radio frequency plasma enhanced chemical vapor deposition
- ECR-PECVD electron-cyclotron-resonance plasma-enhanced chemical vapor deposition
- ICP-ECVD inductively coupled plasma enhanced chemical vapor deposition
- PBS- PECVD plasma beam source plasma enhanced chemical vapor deposition
- Example 1 [0084]
- a CGC is deposited on glass slides, monocrystalline silicon wafers, monocrystalline Si/AIN structures and Sapphire/GaN structures in a parallel- plate capacitive type plasma reactors operating in dual frequency or reactive ion- etching (RIE) configurations at 50°C.
- Deposition processes are conducted by introducing a reactive gas mixture in a deposition chamber.
- the reactive gas mixture initially includes silicon and carbon containing precursors, such as trimethylsilane ((CH 3 ) 3 SiH), and inert gas such as argon (Ar) for depositing the amorphous hydrogenated silicon carbide portion of the CGC structure.
- precursors such as trimethylsilane ((CH 3 ) 3 SiH)
- Ar argon
- an oxidizer such as oxygen (0 2 ) is added to the reactive gas mixture in the deposition chamber for depositing amorphous hydrogenated silicon oxycarbide (SiOC:H) portion of the CGC.
- SiOC:H amorphous hydrogenated silicon oxycarbide
- the composition of the CGC is gradually-changed from hydrogenated oxygen-rich SiOC:H at the interface with polymer layer to hydrogenated oxygen deficient SiOC:H in the direction away from the polymer layer and further to hydrogen-rich amorphous SiC and still further to amorphous SiC with less hydrogen content at the opposite interface with the transparent semiconductor.
- the reactive gas mixture initially includes a silicon containing precursor, such as monosilane (SiH 4 ), a carbon-containing precursor, such as ethylene (C 2 H 4 ), hydrogen (H 2 ), and an inert gas such as argon (Ar) for depositing the amorphous hydrogenated silicon carbide portion of the CGC structure.
- a silicon containing precursor such as monosilane (SiH 4 )
- a carbon-containing precursor such as ethylene (C 2 H 4 ), hydrogen (H 2 )
- an inert gas such as argon (Ar)
- Further oxidizers such as nitrous oxide (N 2 0) and oxygen (0 2 ) are added to the reactive gas mixture in the deposition chamber for depositing amorphous hydrogenated silicon oxy carbon nitride (SiOCN:H) portion of the CGC structure.
- the CGC is gradually-changed from hydrogenated oxygen and nitrogen rich SiOCN:H at the interface with polymer layer to hydrogenated oxygen and nitrogen deficient SiOCN:H in the direction away from the polymer layer and further to hydrogen-rich SiC and still further to SiC with less hydrogen content at the opposite interface with the transparent semiconductor.
- FTIR Fourier-transformed infrared
- Figure 2 More specifically, the FTIR is used to determine how the gradient of the CGC changes from hydrogenated silicon carbide (SiC:H) to hydrogenated silicon oxycarbonitride (SiOCN:H).
- the FT-IR spectrometer is commercially available from, e.g. Thermo Fisher Scientific Inc. (Waltham, MA) under the trade name of Nexus.
- Compositional change of CGCs in depth is also analyzed by X-ray photoelectron spectroscopy (XPS) and shown in Figures 3A/B. More specifically, XPS spectra are taken by using an instrument from Kratos Analytical Ltd. (Chestnut Ridge, NY).
- the examples are analyzed using a spectroscopic ellipsometer to determine refractive indices and deposition rate.
- the ellipsometer is commercially available from J.A. Wollam Co. Inc (Lincoln, NE).
- the composition, density and optical characteristics of the CGC are changed by varying low frequency (LF) power, while depositing in dual-frequency PECVD reactor configuration.
- LF low frequency
- Higher LF power increases ion energy which affects the intensity of ion bombardment.
- denser coatings with higher refractive index and absorption coefficient (passing through a maximum) are deposited slower by increasing the LF power, as can be seen in Figure 4.
- the composition and optical properties of various SiOC:H coatings are changed by varying the oxygen gas flow rate.
- 0 2 flow rate typically changes optical properties and deposition rate of the CGC.
- FIG 11 it is seen that higher 0 2 flow rate results in higher deposition rate (passing through a maximum), lower absorption coefficient and refractive index values. This is due to the gradual transition from hydrogenated SiC to hydrogenated SiOC or SiOCN expressed by changes in the FTIR Si-C, Si-0 and Si-N stretching oscillations as can be seen from the spectra in Figure 2.
- the range of refractive index change realized in the described graded layer is from 1.45 to 3.2.
- a PDMS solution as the polymer layer, is disposed on a CGC followed by subsequent curing.
- Refractive index and thickness of the polymer layer are correspondingly 1.41 and 0.5 mm.
- Figure 6 the minimized reflectance achieved by this structure from monosilane chemistry is set forth and is compared to uncoated Si wafers, similar wafers coated with only the PDMS encapsulant, and single antireflective coatings disposed on similar wafers.
- a similar comparison is made for a CGC formed from trimethylsilane chemistry.
- Figure 9 includes data that shows reduced Fresnel reflection loss for Si/AIN structures, as LEDs, that include the CGC of this disclosure. Minimized light reflection for these same structures is shown in Figure 10 for the particular wavelength range 420-480 nm.
- Figure 14 shows bi-layer CGC-polymer antireflective structure design relative to refractive index and thickness including a second order exponential model fit.
- one or more compounds, components, method steps, etc. as set forth in PCT/US2010/049829, which is expressly incorporated herein by reference in its entirety, may be used in whole or in part with any one or more portions of the instant disclosure.
- the symbol "+” used herein describes that values may vary by “+” or “-” the number described after the "+” symbol.
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Abstract
A light emitting diode module includes a transparent semiconductor having a refractive index of 2.7 ± 1.2, a polymer layer disposed on the transparent semiconductor and having a refractive index of 1.5 ± 0.1, and a compositional graded coating (CGC) disposed on the transparent semiconductor and sandwiched between the transparent semiconductor and the polymer layer. The CGC has a thickness and a refractive index varying along the thickness from a first refractive index from (2.2 ± 0.5 to 3.3 ± 0.4) at a first end to a second refractive index of 1.5 ± 0.2 at a second end adjacent to the polymer layer. The CGC also includes a gradient including SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) along the thickness. The module is formed by continuously depositing the CGC on the transparent semiconductor using chemical vapor deposition, and subsequently disposing the polymer layer on the CGC.
Description
METHOD OF FORMING A LIGHT EMITTING DIODE MODULE
[0001] The disclosure relates to a method of forming a light emitting diode module that includes a compositional graded coating comprising a gradient including SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) along the thickness.
[0002] Optoelectronic semiconductors, and electronic articles that include such semiconductors, are well known in the art. Common optoelectronic semiconductors include light emitting diodes (LEDs). LEDs produce light by a process of electroluminescence, generally include one or more diodes that emit light when activated, and typically utilize either flip chips or wire-bonded chips that are connected to diodes to provide power. Many electronic articles also include tie layers, optical layers, substrates, superstrates, and/or additional materials to provide protection from environmental factors.
[0003] LED efficiency is related to an amount of useful light produced and emitted based on a certain electrical input. Uncoated optoelectronic semiconductors tend to exhibit a high refractive index relative to open air which impedes passages of photons at sharp angles relative to the surface of the optoelectronic semiconductor that contacts the air. This property affects the light transmission efficiency of the LEDs. The transmission of useful light can be limited by optical interference, Fresnel and total internal reflection, and absorption of the light by the optical layers, tie layers, substrates, and superstrates, in addition to other factors.
[0004] Different technologies have been developed to increase transmission of light from LEDs. These technologies include texturing surfaces, adding layers having intermediate indices of refraction to the electronic articles, and including antireflective coatings in the electronic articles. Antireflective coatings minimize reflection at interfaces through destructive interference of reflected light, thereby improving optical properties. Antireflective coatings are typically applied on textured surfaces to further reduce reflection. Typically, antireflective coatings are designed to minimize absorption and maximize light transmission, designed to have good adhesion and durability, designed to have passivation functions, and designed to be produced at low cost.
[0005] Light reflection and refraction depend on the angle of light incidence. The critical angle 0C is the angle of light incidence above which total internal reflection
occurs - the light is completely reflected back by the boundary (interface). The larger the critical angel 0C, the more light will escape the LED. One method of increasing the 0C is by increasing the refractive index of the surrounding medium, Since the light exiting the LED tends to be wide-angle distributed, antireflective coatings can be used but usually need to be efficient over a broad range of angles of light incidence. However, single-layer antireflective coatings provide minimum reflection at a specific wavelength and angle and tend to only be effective for small ranges of angles of incident light. Moreover, conventional antireflective coatings that include silicon oxide and nitride are prone to formation of defects at various interfaces because of high temperatures or plasma powers required for deposition. Accordingly, there remain opportunities for improvement.
SUMMARY OF THE DISCLOSURE
[0006] This disclosure provides a light emitting diode module that includes a transparent semiconductor having a refractive index of 2.7 + 1.2, a polymer layer disposed on the transparent semiconductor and having a refractive index of 1.5 + 0.2, and a compositional graded coating (CGC) disposed on the transparent semiconductor and sandwiched between the transparent semiconductor and the polymer layer. The CGC has a thickness and a refractive index varying along the thickness from a first refractive index from (2.2 + 0.5 to 3.3 + 0.4) at a first end to a second refractive index of 1.5 + 0.2 at a second end adjacent to the polymer layer. The CGC also includes a gradient including SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) along the thickness. This disclosure also provides a method of forming the module wherein the method includes continuously depositing the CGC on the transparent semiconductor using chemical vapor deposition, and subsequently disposing the polymer layer on the CGC.
DESCRIPTION OF THE FIGURES
[0007] Figure 1A is a side view of one embodiment of the module of this disclosure including a polymer layer disposed on, and spaced apart from, a transparent semiconductor, and a compositional graded coating disposed on, and in direct contact with, the transparent semiconductor, and sandwiched between the transparent semiconductor and the polymer layer.
[0008] Figure IB is a side view of one embodiment of the module of this disclosure including a polymer layer disposed on, and spaced apart from, an LED as a
transparent semiconductor, and a compositional graded coating disposed on, and in direct contact with, the LED, and sandwiched between the LED and the polymer layer.
[0009] Figure 2 is an FT-IR spectrum of SiC:H and SiOCN:H films with varying contents of nitrogen and oxygen.
[0010] Figure 3A is an XPS compositional profile of elemental concentration as a function of thickness of a compositional graded coating of this disclosure formed using (CFL^SiH as a source of Si-C.
[0011 ] Figure 3B is an XPS compositional profile of elemental concentration as a function of thickness of a compositional graded coating of this disclosure formed using SiH4 and C2H4 as sources of Si-C.
[0012] Figure 4 is a line graph of refractive index, deposition rate, and absorption coefficient of coatings as functions of low frequency power in a dual-frequency PECVD reaction chamber using (CFL^SiH.
[0013] Figure 5 is a line graph of refractive index, deposition rate, and absorption coefficient of coatings as functions of oxygen flow rate in a dual-frequency PECVD reaction chamber using (CFL^SiH.
[0014] Figure 6 is a spectra of reflection as a function of wavelength of a bare Si substrate (BareSi), the same substrate including a polymer layer disposed thereon (SiEnc), a single layer antireflective coating with a polymer layer (ARC/Enc), and two different CGCs of this disclosure including a polymer layer disposed thereon (CGClEnc and CGC2Enc).
[0015] Figure 7 is a line graph of reflectance of a bare Si substrate (SiRef - R), the same Si substrate including a CGC (formed using (CH3)3SiH) of this disclosure disposed thereon (CGC - R), the same Si substrate including the same CGC and the polymer layer (CGC.Enc - R), a glass reference transmittance (Glass Ref -T) and the same glass reference including a CGC of this disclosure (CGC - T).
[0016] Figure 8 is a line graph of photoluminescent intensity (cps) as a function of wavelength of a CGC of this disclosure (formed using (CFL^SiH) with a three- component Gaussian model fit and a bare Si reference wafer.
[0017] Figure 9 is a line graph of light reflection ( ) as a function of the wavelength of light of A1N disposed on a Si substrate, a first CGC of this disclosure (formed
using (CH3)3SiH) disposed on the AIN/Si, and a second based CGC of this disclosure (formed using (CH3)3SiH) disposed on the AIN/Si.
[0018] Figure 10 is a line graph of reflection as a function of the wavelength of light of A1N disposed on a Si substrate, a first CGC of this disclosure (formed using (CH3)3SiH) disposed on the AIN/Si, and a second CGC of this disclosure (formed using (CH3)3SiH) disposed on the AIN/Si.
[0019] Figure 11A is a reflectance spectra of a A^C GaN reference, a first CGC of this disclosure (formed using (CF^^SiH) disposed on the A^C GaN reference, a second CGC of this disclosure (formed using (CH3)3SiH) disposed on the Al2C>3/GaN reference, and a third CGC of this disclosure (formed using SiH4).
[0020] Figure 1 IB is a transmittance spectra of a A^C GaN reference, a first CGC of this disclosure (formed using (CF^^SiH) disposed on the A^C GaN reference, a second CGC of this disclosure (formed using (CF^^SiH) disposed on the A^C GaN reference, and a third CGC of this disclosure (formed using SiH4).
[0021] Figure 12A is a reflectance spectra of a A^C GaN reference, a first CGC of this disclosure (formed using (CF^^SiH) disposed on the A^C GaN reference, and a second CGC of this disclosure (formed using (CF^^SiH) disposed on the A^C GaN reference and also including a polymer layer disposed on the second CGC.
[0022] Figure 12B is a transmittance spectra of a A^C GaN reference, a first CGC of this disclosure (formed using (CF^^SiH) disposed on the A^C GaN reference, and a second CGC of this disclosure (formed using (CF^^SiH) disposed on the A^C GaN reference and also including a polymer layer disposed on the second CGC.
[0023] Figure 13 A is a reflectance spectra of a Al2C>3/GaN reference, a first CGC of this disclosure (formed using SiH4) disposed on the Al2C>3/GaN reference, and a second CGC of this disclosure (formed using SiH4) disposed on the Al2C>3/GaN reference and also including a polymer layer disposed on the second CGC.
[0024] Figure 13B is a transmittance spectra of a Al2C>3/GaN reference, a first CGC of this disclosure (formed using SiH4) disposed on the Al2C>3/GaN reference, and a second CGC of this disclosure (formed using SiH4) disposed on the Al2C>3/GaN reference and also including a polymer layer disposed on the second CGC.
[0025] Figure 14 is a graph of refractive index of a compositional graded coating disposed on GaN as a function of thickness including a third order exponential model fit.
[0026] Figure 15 is an example of a 2-dimensional gradient.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0027] This disclosure provides a light emitting diode (LED) module and a method of forming the module. The module tends to be a solid-state device that emits light in a spectral range when a forward bias is applied. The wavelength of the emitted light is typically dependent on the energy bandgap (Eg) of a transparent semiconductor used in the active region of the device. In one embodiment, the transparent semiconductor includes a p-n junction with a multiple-quantum-well active region and carrier- confining layers. The module typically has a light reflection of less than 10, 7, 5, 4, 3, 2, or 1% over a range of wavelengths from about 300 to about 1700 nanometers. The light reflection is typically measured using a spectrophotometer and/or an ellipsometer such as a Cary 5000 UV-Vis-NIR spectrophotometer commercially available from Agilent Technologies Inc. (Santa Clara, California).
[0028] The module may be alternatively described as a solid state light (e.g. a solid state light that includes an LED) or as solid state lighting and can be used in any application including, but not limited to, instrument panels & switches, courtesy lighting, turn and stop signals, household appliances, VCR/DVD/ stereo/audio/video devices, toys/games instrumentation, security equipment, switches, architectural lighting, signage (channel letters), machine vision, retail displays, emergency lighting, neon and bulb replacement, flashlights, accent lighting full color video, monochrome message boards, in traffic, rail, and aviation applications, in mobile phones, PDAs, digital cameras, lap tops, in medical instrumentation, bar code readers, color & money sensors, encoders, optical switches, fiber optic communication, and combinations thereof.
[0029] The module includes a transparent semiconductor. The transparent semiconductor is not particularly limited and may be further described as one or more of semiconductor LEDs, organic LEDs, polymer LEDs, quantum dot LEDs, infrared LEDs, visible light LEDs (including colored and white light), ultraviolet LEDs, and combinations thereof. The transparent semiconductor may include a single layer or multiple layers. The transparent semiconductor is typically at least 75, 80, 85, 90, 95, 96, 97, 98, or 99% transparent to the ultraviolet (UV), visible and/or infrared (IR) light typically measured using a spectrophotometer and/or an ellipsometer. The transparent semiconductor may alternatively include or be further defined as AI2O3,
SiC, a semiconductor chosen from Group III and/or Group IV from the periodic table, and/or combinations thereof. In various embodiments, the transparent semiconductor is chosen from GaN, AlGaN, A1N, GaAs, AlGaAs, InP, InGaAsP, and combinations thereof. The transparent semiconductor has a refractive index of (about) 1.5 to 3.9, i.e., 2.7 + 1.2, 1.1, 1, 0.75, 0.5, 0.25, or 0.1. In various embodiments, the transparent semiconductor has a thickness from 0.2 to 2.0, from 0.4 to 1.8, from 0.6 to 1.6, from 0.8 to 1.4, or from 1.0 to 1.2, mm. The module may also include one or more layers or components known in the art as typically associated such modules. For example, the module may include one or more drivers, optics, heat sinks, housings, lenses, power supplies, fixtures, wires, electrodes, circuits, and the like.
[0030] The module may include two, three, or multiple (layers of) transparent semiconductors, each of which may independently be the same or different from those described above. Typically, several layers of transparent semiconductors are utilized to form an LED. In one embodiment, a top (e.g. outermost) transparent semiconductor, of the multiple layers, is further defined as a light emitting diode. In other words, a top layer of multiple layers of the transparent semiconductor may be further defined as a light emitting diode.
[0031] Moreover, the module may include a phosphor. The phosphor is not particularly limited and may include any known in the art. In one embodiment, the phosphor is made from a host material and an activator, such as copper-activated zinc sulfide and silver- activated zinc sulfide. Suitable but non-limiting host materials include oxides, nitrides and oxynitrides, sulfides, selenides, halides or silicates of zinc, cadmium, manganese, aluminum, silicon, or various rare earth metals. Additional suitable phosphors include, but are not limited to, Zn2SiC>4:Mn (Willemite); ZnS:Ag+(Zn,Cd)S:Ag; ZnS:Ag+ZnS:Cu+Y202S:Eu; ZnO:Zn; KC1; ZnS:Ag,Cl or ZnS:Zn; (KF,MgF2):Mn; (Zn,Cd)S:Ag or (Zn,Cd)S:Cu; Y202S:Eu+Fe203, ZnS:Cu,Al; ZnS:Ag+Co-on-Al203;(KF,MgF2):Mn;
(Zn,Cd)S:Cu,Cl; ZnS:Cu or ZnS:Cu,Ag; MgF2:Mn; (Zn,Mg)F2:Mn; Zn2Si04:Mn,As; ZnS:Ag+(Zn,Cd)S:Cu; Gd202S:Tb; Y202S:Tb; Y3Al50i2:Ce; Y2Si05:Ce; Y3Al50i2:Tb; ZnS:Ag,Al; ZnS:Ag; ZnS:Cu,Al or ZnS:Cu,Au,Al; (Zn,Cd)S:Cu,Cl+(Zn,Cd)S:Ag,Cl; Y2Si05:Tb; Y2OS:Tb; Y3(Al,Ga)50i2:Ce; Y3(Al,Ga)50i2:Tb; InB03:Tb; InB03:Eu; InB03:Tb+InB03:Eu;
InB03:Tb+InB03:Eu+ZnS:Ag; (Ba,Eu)Mg2Al16027; (Ce,Tb)MgAlnOi9;
BaMgAl10Oi7:Eu,Mn; BaMg2Al16027:Eu(II); BaMgAl10Oi7:Eu,Mn;
BaMg2Al16027:Eu(II),Mn(II); Ceo.67Tbo.33MgAlnOi9:Ce,Tb; Zn2Si04:Mn,Sb203; CaSi03:Pb,Mn; CaW04 (Scheelite); CaW04:Pb; MgW04; (Sr,Eu,Ba,Ca)5(P04)3Cl; Sr5Cl(P04)3:Eu(II); (Ca,Sr,Ba) (P04)2Cl2:Eu; (Sr,Ca,Ba)10(PO4)6Cl2:Eu;
Sr2P207:Sn(II); Sr6P5BO20:Eu; Ca5F(P04)3:Sb; (Ba,Ti)2P207:Ti;
3Sr3(P04)2.SrF2:Sb,Mn; Sr5F(P04)3:Sb,Mn; Sr5F(P04)3:Sb,Mn; LaP04:Ce,Tb; (La,Ce,Tb)P04;(La,Ce,Tb)P04:Ce,Tb; Ca3(P04)2.CaF2:Ce,Mn; (Ca,Zn,Mg)3 (P04)2:Sn; (Zn,Sr)3(P04)2:Mn; (Sr,Mg)3(P04)2:Sn; (Sr,Mg)3(P04)2:Sn(II); Ca5F(P04)3:Sb,Mn; Ca5(F,Cl)(P04)3:Sb,Mn; (Y,Eu)203; Y203:Eu(III); Mg4(F)Ge06:Mn; Mg4(F)(Ge,Sn)06:Mn; Y(P,V)04:Eu; YV04:Eu; Y202S:Eu; 3.5 MgO · 0.5 MgF2 · Ge02 :Mn; Mg5As2On:Mn; SrAl207:Pb; LaMgAlnOi9:Ce; LaP04:Ce; SrAl120i9:Ce; BaSi205:Pb; SrFB203:Eu(II); SrB407:Eu; Sr2MgSi207:Pb; MgGa204:Mn(II); Gd202S:Tb; Gd202S:Eu; Gd202S:Pr; Gd202S:Pr,Ce,F; Y202S:Tb; Y202S:Eu; Y202S:Pr; Zn(0.5)Cd(0.4)S:Ag; Zn(0.4)Cd(0.6)S:Ag; CdW04; CaW04; MgW04; Y2Si05:Ce;YA103:Ce; Y3Al50i2:Ce; Y3(Al,Ga)50i2:Ce; CdS:In; ZnO:Ga; ZnO:Zn; (Zn,Cd)S:Cu,Al; ZnS:Cu,Al,Au; ZnCdS:Ag,Cu; ZnS:Ag; anthracene, EJ- 212, Zn2Si04:Mn; ZnS:Cu; NaI:Tl; CsI:Tl; LiF/ZnS:Ag; LiF/ZnSCu,Al,Au, and combinations thereof.
[0032] The phosphor may be present in any portion of the module. The phosphor may be present as a discrete layer in the module or as part of an independent composition. In other words, the phosphor may be present in an independent layer or may be combined with a composition, e.g. in a gradient pattern, homogeneously dispersed throughout, or present in higher concentrations in some areas of the composition and in lower concentration in other areas of the composition. In another embodiment, the phosphor is present in a lens of the module.
[0033] The module may also include a release liner. The release liner may be any known in the art such as siliconized PET or a fluorinated liner. These release liners are typically smooth but can also be textured e.g. in or as an anti-reflective surface.
[0034] The module also includes a polymer layer that is disposed on the transparent semiconductor and that has a refractive index of 1.3 to 1.8, i.e., 1.5 + 0.05, 0.1, 0.15, 0.2, or + 0.2, or 0.3, as determined using a spectroscopic ellipsometer refractometer. In another embodiment, the refractive index of the polymer layer is approximately matched to the refractive index of the compositional graded coating, e.g. ±0.1,
described in greater detail below. The polymer layer also typically has a light transparency of at least 85, 90, 95, 96, 97, 98, 99, or 99.5, percent, as determined using a spectrophotometer. In one embodiment, the polymer layer has a light transparency of about 100 percent (- 10, 5, 2, 1, 0.75, 0.5, 0.25 ). The terminology "disposed on" includes the polymer layer disposed on and in direct contact with the transparent semiconductor or on and spaced apart from the transparent semiconductor yet still disposed thereon, as set forth in Figure 1. Typically, the polymer layer is disposed on and spaced apart from the transparent semiconductor.
[0035] The polymer layer may have a thickness of at least 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, or 125, μιη. Alternatively, the polymer layer may have a thickness from 50 to 150, from 60 to 140, from 70 to 130, from 80 to 120, from 90 to 110, from 50 to 250, from 60 to 350, from 70 to 450, from 80 to 550, or from 100 to 1000, μιη. In one embodiment, the polymer layer has a thickness of about 300 μιη. In various embodiments, the polymer layer has a thickness that is about the same or longer than the coherence length of emitted light, whether visible light, UV light, and IR light. This thickness minimizes interference effects due to an optical path length greater than the coherence length of emitted light. If the polymer layer is overly thinned, increased interference may occur which may cause coloring and/or spectral effects.
[0036] The polymer layer may be formed from and/or include an inorganic compound, and organic compound, or a mixture of organic and inorganic compounds. These compounds may or may not require curing. Alternatively, the polymer layer may be formed from and/or include metals, polymers, plastics, silicones, glass, sapphire, and the like so long as the refractive index is as described above. In various embodiments, the polymer layer is ethylene vinyl acetate (EVA), glass, a silicone, and/or an acrylate. Typically, the polymer layer is transparent to light as determined using a spectrophotometer. The polymer layer may be formed from a curable composition including silicon atoms. In one embodiment, the curable composition includes a hydrosilylation curable polydimethylsiloxane (PDMS). In other embodiments, the polymer layer may be as described in one or more of PCT/US09/01623, PCT/US09/01621, and/or PCT/US09/62513, each of which is expressly incorporated herein by reference. The polymer layer may be an inner layer or an outermost layer of the module.
[0037] The module may include multiple polymer layers, i.e., a second and optionally a third polymer layer, or more. Any additional polymer layer may be the same or different from the polymer layer described above. In one embodiment, the module includes the polymer layer described above and a second polymer layer. Further, the polymer layer may be transparent to UV and/or visible light and the second (or additional) polymer layers may be transparent to UV and/or visible light.
[0038] The module also includes a compositional graded coating (CGC) that is disposed on the transparent semiconductor and sandwiched between the transparent semiconductor and the polymer layer, as set forth in Figure 1. Just as above, the terminology "disposed on" describes the CGC disposed on and in direct contact with the transparent semiconductor. This terminology also describes the CGC spaced apart from the transparent semiconductor, yet still disposed thereon. The module may include two or more CGCs that may be the same or different from one another and each of which may be disposed in any location in the module.
[0039] The CGC has a thickness which is typically from 50 to 1000, from 50 to 950, from 100 to 900, from 150 to 850, from 200 to 800, from 250 to 750, from 300 to 700, from 350 to 650, from 400 to 600, from 450 to 550, from 50 to 750, from 100 to 500, from 150 to 450, from 200 to 300, from 250 to 450, from 350 to 450, about 400, about 450, or about 500, nm. In various embodiments, the CGC has a thickness from 50 to 400 nanometers which is typically chosen to reduce light absorption. In other embodiments, the CGC has a thickness from 60 to 390, from 70 to 380, from 80 to 370, from 90 to 360, from 100 to 350, from 110 to 340, from 120 to 330, from 120 to 320, from 130 to 310, from 140 to 300, from 150 to 290, from 160 to 280, from 170 to 270, from 180 to 260, from 190 to 250, from 200 to 240, or from 210 to 230, nm.
[0040] The CGC has a thickness and a refractive index varying along the thickness from a first refractive index from (1.7 to 3.9, i.e., 2.2 + 0.5 to 3.3 + 0.4) at a first end to a second refractive index of 1.3 to 1.7, i.e., 1.5 + 0.2, at a second end adjacent to the polymer layer. The first refractive index may be alternatively described as from 2.25 to 3.15, from 2.3 to 3.1, from 2.35 to 3.15, from 2.4 to 3.1, from 2.45 to 3.05, from 2.5 to 3, from 2.55 to 2.95, from 2.6 to 2.9, from 2.65 to 2.85, from 2.7 to 2.8, or from 2.75 to 2.8, each + 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, or 0.05. The second refractive index may be alternatively described as 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1. The first end may be further defined as an interface between
the CGC and the transparent semiconductor. Alternatively, the first end may be further defined as an interface between the CGC and an intermediate layer, which is described in greater detail below. The second end may be further defined as an interface between the CGC and the polymer layer.
[0041] The refractive index of the CGC at a particular point along the thickness is typically determined by instantaneous deposition conditions. This refractive index corresponds to the refractive index of a homogeneous coating deposited using identical, but static, deposition conditions for the full coating thickness.
[0042] In one embodiment, the CGC includes a gradient of the refractive indices described above. In another embodiment, the CGC includes a gradient of SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) along the thickness, e.g. with varying hydrogen content and/or Si to C and/or O to Si compositional ratios. In other embodiments, the CGC includes a gradient of refractive indices and/or a gradient of SiC:H and SiOCN:H; SiC:H and SiOC:H; or SiC:H and Si:H. In another embodiment, the CGC includes a gradient of refractive indices and/or a gradient of Si:H, SiC:H, SiOCN:H, and SiOC:H. In still another embodiment, the CGC includes a gradient of a carbide and an oxycarbide along the thickness. In one embodiment, carbide is further defined as hydrogenated silicon carbide (SiC:H) and the oxycarbide is further defined as hydrogenated silicon oxycarbide (SiOC:H). The gradient, in whole or in part, can proceed from SiC:H to SiOCN:H, from SiC:H to SiOC:H, from SiC:H to Si:H, from SiOCN:H to SiOC:H, from SiOCN:H to Si:H, from SiOC:H to Si:H, from Si:H to SiOC:H, from Si:H to SiOCN:H, from Si:H to SiC:H, any reverse order thereof, or any combination thereof.
[0043] In still another embodiment, the CGC includes both a gradient of the refractive indices and of the amounts of SiC:H and (SiOCN:H; SiOC:H; and/or Si:H). The gradients of the refractive indices and of the amounts of SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) may independently be continuous (e.g. uninterrupted and/or consistently changing) or stepped, e.g. discontinuous or changing in one or more steps. The terminology "gradient" typically describes a graded change in the magnitude of the refractive indices and/or the amounts of SiC:H and (SiOCN:H; SiOC:H; and/or Si:H), e.g. from lower to higher values or vice versa. The gradient may be further defined as a vector field which points in the direction of the greatest rate of increase and whose magnitude is the greatest rate of change. The gradient may
be further defined as a series of 2 dimensional vectors at points on the CGC with components given by the derivatives in horizontal and vertical directions. At each point on the CGC, the vector points in the direction of largest possible intensity increase, and the length of the vector corresponds to the rate of change in that direction. An example of a 2-dimensional gradient is set forth in Figure 15.
[0044] In various embodiments, the CGC has a continuous gradient with one extreme of the gradient selected to approximately match the refractive index of the transparent semiconductor or the intermediate layer, described in greater detail below. In one embodiment, the index of refraction of the CGC smoothly shifts from approximately matching (e.g. + 0.2) the refractive index of the intermediate layer to a refractive index that approximately matches (e.g. + 0.2) that of the polymer layer to avoid or minimize significant discontinuity in optical characteristics at interfaces therebetween. In another embodiment, the CGC includes hydrogenated silicon (Si:H) at the interface with the transparent semiconductor and then the continuous gradient gradually changes to hydrogenated silicon carbide (SiC:H) and then to hydrogenated silicon oxycarbonitride (SiOCN:H) near the interface with the polymer layer. Alternatively, the CGC may include hydrogenated silicon carbide (SiC:H) (e.g. at an interface with the transparent semiconductor) and then gradually change to hydrogenated silicon oxycarbonitride (SiOCN:H) near the interface with the polymer layer. Typically, in this embodiment, the module includes the intermediate layer including the Si:H, as described in greater detail below. Also in this embodiment, the hydrogenated silicon carbide (SiC:H) is typically present near the interface with the intermediate layer (e.g. the Si:H).
[0045] Changing the composition and/or density of the CGC along with grading the optical impedance of the CGC may provide a smooth transition between the transparent semiconductor and the polymer layer approximately matching the optical parameters (e.g. + 0.2) of each at the relevant interfaces. Apart from the refractive indices described above, the CGC may have a variety of physical properties that benefit performance of the module. In various embodiments, the CGC emits light having a wavelength from 375 to 675, from 400 to 650, from 425 to 625, from 450 to 600, from 475 to 575, from 500 to 550, from 525 to 550, from 450 to 700, or from 500 to 600, nm, when excited with light having a wavelength from 300 to 450, from
300 to 400, from 310 to 390, from 320 to 380, from 330 to 370, from 340 to 360, or from 340 to 350, nm.
[0046] The module may also include Si:H disposed between the polymer layer and the transparent semiconductor. The Si:H may be included in the intermediate layer disposed between the CGC and the transparent semiconductor. The intermediate layer may have a refractive index from 3 to 3.3 + 0.2 or from 3 to 3.5 + 0.2. In one embodiment wherein the module includes the intermediate layer, the CGC has a refractive index varying along the thickness from the first refractive index of 2.2 + 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, or 0.05 at the first end to the second refractive index of 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1 at the second end adjacent to the polymer layer. Alternatively, the Si:H may be present in the CGC such that the gradient includes Si:H, SiC:H and optionally SiOC:H and/or SiOCN:H. Typically, in this embodiment, the CGC has a refractive index varying along the thickness from the first refractive index of 3.3 + 0.5, 0.4, 0.3, 0.2, or 0.1 at the first end to the second refractive index of 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1 at the second end adjacent to the polymer layer. The Si:H may also be present both in the gradient and in the intermediate layer.
[0047] The module may also include the intermediate layer, e.g. an inorganic layer. In one embodiment, the intermediate layer is disposed on the transparent semiconductor and sandwiched between the transparent semiconductor and the CGC. The terminology "disposed on" includes the intermediate layer disposed on and in direct contact with the transparent semiconductor. This terminology also includes the intermediate layer spaced apart from the transparent semiconductor yet still disposed thereon.
[0048] The intermediate layer is not particularly limited and may include any inorganic (i.e., non-organic) element or compound known in the art. The intermediate layer may include a content of organic compounds in addition to inorganic compounds. In one embodiment, the intermediate layer includes silicon carbide. In other embodiments, the intermediate layer includes Si:H. The intermediate layer may be used to compatibilize the CGC and the transparent semiconductor. The intermediate layer may have a refractive index within 1, 2, 3, 4, 5, 10, 15, 20, or 25 percent to that of the CGC and/or to that of the transparent semiconductor. For
example, the intermediate layer may have a refractive index from 3 to 3.3 + 0.2 or from 3 to 3.5 + 0.2.
[0049] In one embodiment wherein the module includes the intermediate layer, the CGC has a refractive index varying along the thickness from the first refractive index of 2.2 + 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, or 0.05 at the first end to the second refractive index of 1.45 + 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1 at the second end adjacent to the polymer layer. Alternatively, the Si:H may be present in the compositional graded coating such that the gradient includes Si:H, SiC:H and SiOCN:H. Typically, in this embodiment, the CGC has a refractive index varying along the thickness from the first refractive index of 3.3 + 0.5, 0.4, 0.3, 0.2, or 0.1 at the first end to the second refractive index of 1.45 ± 0.01, 0.02, 0.03, 0.04, 0.06, 0.07, 0.08, 0.09, or 0.1 at the second end adjacent to the polymer layer. The Si:H may also be present both in the gradient and in the intermediate layer.
[0050] The module may also include a superstrate and/or substrate which may independently include any material known in the art. The superstrate may be utilized with the polymer layer. Typically, the substrate provides protection to a rear surface of the module and the superstrate provides protection to a front surface of the module. The substrate and/or superstrate may each be soft and flexible or rigid and stiff. Alternatively, the substrate and/or superstrate may include rigid and stiff segments while simultaneously including soft and flexible segments. The substrate may be transparent to light, may be opaque, or may not transmit light. Most typically, the superstrate allows at least some light to penetrate the module. The substrate and/or superstrate may include glass, stainless steel, metal foils, polyimides, ethylene-vinyl acetate copolymers, and/or organic fluoropolymers such as ethylene tetrafluoroethylene (ETFE), Tedlar® (polyvinylfluoride, available from DuPont), polyester/Tedlar®, Tedlar®/polyester/Tedlar®, polyethylene terephthalate (PET) alone or coated with silicon and oxygen based materials (SiOx), and combinations thereof. In one embodiment, the substrate is selected from the group of polyvinylfluoride and polyethylene. The substrate may alternatively be a PET/SiOx-PET/Al substrate, wherein x is a number having a value from 1 to 4. Still further, the substrate and/or superstrate may include silicone, may consist essentially of silicone and not include, or include less than 1 wt , organic monomers or organic polymers, or may consist of
silicone. The optional silicone chemistry of the substrate and/or superstate may include any type known in the art.
[0051 ] The substrate and/or superstate may be load bearing or non-load bearing. Typically, the substrate is load bearing and the superstate is not load bearing. The substrate is typically a bottom and outermost layer of the module. Bottom layers are typically positioned behind the transparent semiconductor and serve as mechanical support. The superstrate is typically a top and outermost layer of the module and may be oriented towards the light source. If both a substrate and superstrate are utilized, the substrate and superstrate each typically act as outermost layers and sandwich all other components of the module therebetween.
[0052] The module may be free of a "backsheet" and/or "front glass." The terminology "backsheet" typically describes a substrate, as described above. In one embodiment, the backsheet includes metal foils, polyimides, ethylene-vinyl acetate copolymers, and/or organic fluoropolymers such as ethylene tetrafluoroethylene (ETFE), Tedlar® (polyvinylfluoride), polyester/Tedlar®, Tedlar®/polyester/Tedlar®, polyethylene terephthalate (PET) alone or coated with silicon and oxygen based materials (SiOx), and combinations thereof. The "backsheet" may alternatively be the PET/SiOx-PET/Al substrate. However, the module may be free of the "backsheet" and still include one or more compounds or components described above as a substrate. The module may still include a substrate and be free of a "backsheet." The terminology "front glass" typically describes used as a superstrate that allows light to pass through. The module may be free of the "front glass" and still include one or more compounds or components described above as a superstrate. The module may still include a superstrate and be free of "front glass."
[0053] In addition, the module may also include one or more tie layers which may bind one or more other layers to each other. The one or more tie layers may be disposed on the substrate to bind the transparent semiconductor to the substrate and/or one or more other layers. In various embodiments, the module includes multiple tie layers, e.g. first, second, and/or a third tie layer. Any second, third, or additional tie layer may be the same or different from the (first) tie layer. Thus, any second, third or additional tie layer may be formed from the same material or from a different material than the (first) tie layer. The second tie layer may be disposed on the (first) tie layer and/or may be disposed on the transparent semiconductor. The one or more tie layers
are each typically transparent to UV and/or visible light. In one embodiment, the tie layer has high transmission across visible wavelengths, long term stability to UV and provides long term protection to the transparent semiconductor.
[0054] The tie layers typically have a thickness from 1 to 50, more typically from 3 to 30, and most typically from 4 to 15, mils. In various embodiments, the tie layers have a thickness from 1 to 30, from 1 to 25, from 1 to 20, from 3 to 17, from 5 to 10, from 5 to 25, from 10 to 15, from 10 to 17, from 12 to 15, from 10 to 30, or from 5 to 20, mils. Alternatively, the tie layer(s) may be as described in PCT/US09/01623, PCT/US09/01621, and/or PCT/US09/62513, each of which is expressly incorporated herein by reference.
[0055] The method of forming the module includes continuously depositing the CGC on the transparent semiconductor using chemical vapor deposition (CVD) and subsequently disposing the polymer layer on the CGC to form the module. The step of continuously depositing the CGC may be accomplished using plasma-enhanced chemical vapor deposition (PECVD), e.g., in a reactive ion-etching configuration, dual frequency configuration, electron cyclotron resonance configuration or inductively-coupled plasma mode. Any type of CVD known in the art may be utilized.
[0056] The terminology "continuously depositing" typically describes the CVD operating without interruption or with few interruptions. The continuous operation of the CVD minimizes or eliminates formation of additional optical interfaces in the CGC which allows a gradient to be formed with minimized reflection, absorption, and interference and also allows the module to be formed with increased durability and flexibility and optimized optical properties. The step of continuously depositing may occur below room temperature, at room temperature (referred to herein as "RT" and is about 21 to 25°C), or above RT. In various embodiments, the temperature is about 50, 100, 200, 300, or 400, °C.
[0057] Typically, a CVD system is used, such as a PECVD system that mixes precursor gasses in vacuum chambers and excites mixtures of the gases with radio frequency (RF) generators attached to electrodes to create plasmas of ionized gasses. An electrical potential difference between the plasmas and various substrates accelerates ions towards surfaces where they react, e.g. react to form the CGC. Vacuum pressure, electrode power, temperature, and gas flow can be customized, see,
e.g. the Figures. In one embodiment, the PECVD system includes a powered parallel- plate electrode reactor with electrodes powered with two generators. One generator is typically a standard RF generator (also called a high frequency power supply (e.g. 13.56 MHz)) with a power control range of 20W to 600W. The second generator is typically a middle to low frequency (e.g. 380 kHz) power supply with a power range of 20W to 1000W. The PECVD system may also include a third electrode, for example chamber walls.
[0058] The CVD system may operate in a dual frequency configuration (e.g. mode). Operation in the dual frequency configuration typically includes the operation of PECVD at a first and a second frequency simultaneously. The first frequency is typically between 50 and 400 kHz and can range from 60 to 390, from 70 to 380, from 80 to 370, from 90 to 360, from 100 to 350, from 110 to 340, from 120 to 330, from 130 to 320, from 140 to 310, from 150 to 300, from 200 to 290, from 210 to 280, from 220 to 270, from 230 to 260, or from 240 to 250, KHz. In one embodiment, the first frequency ranges between 70 and 400 KHz. In another embodiment, the first frequency is about 380 KHz. The second frequency is typically between 10 MHz and 1, or more than 1, GHz. In various embodiments, the second frequency ranges from 10 to 50, from 10 to 40, from 12 to 30, from 13 to 20, from 13 to 15, or from 13 to 14, MHz. In one embodiment, the second frequency is about 13.56 MHz.
[0059] The power of the electrodes used in the CVD system can be varied. In various embodiments, two electrodes are utilized wherein the power to each electrode may be varied independently. The power to a first electrode typically ranges from 10 to 1000, from 10 to 600, from 50 to 200, from 80 to 160, from 90 to 150, from 100 to 140, from 110 to 130, or about 120, Watts. The first electrode is typically associated with the first frequency described above. The power to a second electrode typically ranges from 10 to 1000, from 10 to 600, from 200 to 400, from 210 to 390, from 220 to 380, from 230 to 370, from 240 to 360, from 250 to 350, from 260 to 340, from 270 to 330, from 280 to 320, from 290 to 310, or about 300, Watts. The second electrode is typically associated with the second frequency described above.
[0060] The second (e.g. high) frequency may influence plasma density due to more efficient displacement current and sheath heating mechanisms. The first (e.g. low) frequency may influence peak ion bombardment energy. Accordingly, separate adjustment and customization of ion bombardment energy and plasma density may be
utilized to influence control of deposition stress and optical properties. In addition, greater control of lattice spacing of the CGC as well as stacking faults in crystal structure, control of pin holes and location of interstitial atoms, and minimization of deposition tension and stress may be customized.
[0061] The step of continuously depositing the CGC may include one or more sub- steps. In various embodiments, the step of continuously depositing includes introducing a source of silicon, such as monosilane (SiH4) or (CH3)3SiH), to the transparent semiconductor, introducing a hydrocarbon gas (e.g. methane, ethylene, acetylene, or any known in the art) to the transparent semiconductor, and introducing at least one of nitrous oxide, oxygen, and carbon dioxide to the transparent semiconductor. The step of introducing "to the transparent semiconductor" may be alternatively defined as introducing "into the plasma" or "into a CVD chamber" wherein the transparent semiconductor is exposed to the plasma and/or the source of the silicon, the hydrocarbon gas, or the other gases, in the CVD chamber. The introduction of the source of silicon allows the CVD process to produce the Si:H of the module and/or gradient. The introduction of the hydrocarbon gas allows the CVD process to produce the SiC:H of the gradient. The introduction of at least one of the nitrous oxide, oxygen, and carbon dioxide allows the CVD process to produce the SiOCN:H of the gradient. The method may alternatively include the step of introducing a source of nitrogen (e.g. nitrous oxide) and/or the step of introducing a source of oxygen (e.g. nitrous oxide and/or oxygen), to the transparent semiconductor (e.g. into the plasma).
[0062] More typically, the source of silicon is introduced at a high power (e.g. above 300 Watts). This step typically forms a first portion of the gradient with a high refractive index (e.g. ~ 2.7 to 3.6). In another embodiment, the method includes the step of increasing pressure (e.g. increasing from 50 to 500 mTorr). Typically, increasing the pressure decreases the refractive index of the gradient that is being formed. In still another embodiment, the method includes the step of decreasing power and increasing pressure to continue to form the CGC.
[0063] In various embodiments, the total gas flow can range from 200 to 3,000, from 400 to 2,000, or from 450 to 850, standard cubic centimeters per minutes (seem). The temperature can range from 20 to 400, from 30 to 250, or from 30 to 80°C. The
pressure can range from 20 to 2000, from 20 to 1000, from 80 to 800, from 50 to 500, or from 90 to 200, mTorr.
[0064] The method also includes the step of disposing the polymer layer on the CGC. The step of disposing the polymer layer may be further defined as disposing a curable composition on the CGC and then either partially or completely curing the curable composition to form the polymer layer. Alternatively, the polymer layer may be disposed on the CGC without any additional curing. The polymer layer and/or curable composition may be applied using any suitable application (dispensing) method known in the art including spray coating, flow coating, curtain coating, dip coating, extrusion coating, knife coating, screen coating, laminating, melting, pouring, and combinations thereof. In one embodiment, the polymer layer is formed from a liquid and the step of disposing the polymer layer is further defined as disposing a liquid on the CGC and curing the liquid on the CGC to form the polymer layer. In another embodiment, the curable composition is supplied to a user as a multi-part system, e.g. including first and second parts. The first and second parts may be mixed immediately prior to use. Alternatively, each component and/or a mixture of components may be applied individually.
[0065] In one embodiment, the polymer layer is formed from the curable composition and the method further includes the step of partially curing, e.g. "pre-curing," the curable composition to form the polymer layer. In another embodiment, the method further includes the steps of applying the curable composition to the CGC and curing the curable composition to form the polymer layer. In one embodiment, the curable composition is cured prior to the step of disposing the polymer layer on the substrate. The curable composition may be cured at any temperature, e.g. from 25 to 200 °C. The curable composition may also be cured for any time, e.g. from 1 to 600 seconds. Alternatively, the curable composition may be cured in a time of greater than 600 seconds, as determined by one of skill in the art.
[0066] Examples of suitable curable silicone compositions include hydrosilylation- curable silicone compositions, condensation-curable silicone compositions, radiation- curable silicone compositions, and peroxide-curable silicone compositions.
[0067] A hydrosilylation-curable silicone composition typically includes an organopolysiloxane having an average of at least two silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms per molecule; an organosilicon compound in an
amount sufficient to cure the organopolysiloxane, wherein the organosilicon compound has an average of at least two silicon-bonded hydrogen atoms or silicon- bonded alkenyl groups per molecule capable of reacting with the silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the organopolysiloxane; and a catalytic amount of a hydrosilylation catalyst.
[0068] A condensation-curable silicone composition typically includes an organopolysiloxane having an average of at least two silicon-bonded hydrogen atoms, hydroxy groups, or hydrolysable groups per molecule and, optionally, a cross-linking agent having silicon-bonded hydrolysable groups and/or a condensation catalyst.
[0069] A radiation-curable silicone composition typically includes an organopolysiloxane having an average of at least two silicon-bonded radiation- sensitive groups per molecule and, optionally, a cationic or free -radical photoinitiator depending on the nature of the radiation-sensitive groups in the organopolysiloxane.
[0070] A peroxide-curable silicone composition typically includes an organopolysiloxane having silicon-bonded unsaturated aliphatic hydrocarbon groups and an organic peroxide.
[0071 ] The silicone composition can be cured by exposing the composition to ambient temperature, elevated temperature, moisture, or radiation, depending on the type of curable silicone composition.
[0072] When the curable silicone composition is a hydrosilylation-curable silicone composition, the silicone composition can be cured by exposing the composition to a temperature from RT to 250 °C, alternatively from RT to 150 °C, alternatively from RT to 115 °C, at atmospheric pressure. The silicone composition is generally heated for a length of time sufficient to cure (cross-link) the organopolysiloxane. For example, the film is typically heated at a temperature from 100 to 150 °C for a time from 0.1 to 3 h.
[0073] When the curable silicone composition is a condensation-curable silicone composition, the conditions for curing the composition depend on the nature of the silicon-bonded groups in the organopolysiloxane. For example, when the organopolysiloxane contains silicon-bonded hydroxy groups, the composition can be cured (i.e., cross-linked) by heating the composition. The composition can typically be cured by heating it at a temperature from 50 to 250 °C, for a period from 1 to 50 h. When the condensation-curable silicone composition includes a condensation catalyst,
the composition can typically be cured at a lower temperature, e.g., from RT to 150 °C.
[0074] When the curable silicone composition is a condensation-curable silicone composition including an organopolysiloxane having silicon-bonded hydrogen atoms, the composition can be cured by exposing the composition to moisture or oxygen at a temperature from 100 to 450 °C for a period from 0.1 to 20 h. When the condensation-curable silicone composition contains a condensation catalyst, the composition can typically be cured at a lower temperature, e.g., from RT to 400°C.
[0075] Further, when the curable silicone composition is a condensation-curable silicone composition including an organopolysiloxane having silicon-bonded hydrolysable groups, the composition can be cured by exposing the composition to moisture at a temperature from RT to 250°C, alternatively from 100 to 200°C, for a period from 1 to 100 h. For example, the silicone composition can typically be cured by exposing it to a relative humidity of 30% at a temperature from RT to 150 °C, for a period from 0.5 to 72 h. Cure can be accelerated by application of heat, exposure to high humidity, and/or addition of a condensation catalyst to the composition.
[0076] When the curable silicone composition is a radiation-curable silicone composition, the composition can be cured by exposing the composition to an electron beam. Typically, the accelerating voltage is from about 0.1 to 100 keV, the vacuum is from about 10 to 10~3 Pa, the electron current is from about 0.0001 to 1 ampere, and the power varies from about 0.1 watt to 1 kilowatt. The dose is typically from about 100 microcoulomb/cm^ to 100 coulomb/cm^, alternatively from about 1 to 10 coulombs/cm^. Depending on the voltage, the time of exposure is typically from about 10 seconds to 1 hour.
[0077] Also, when the radiation-curable silicone composition further includes a cationic or free radical photoinitiator, the composition can be cured by exposing it to radiation having a wavelength from 150 to 800 nm, alternatively from 200 to 400 nm, at a dosage sufficient to cure (cross-link) the organopolysiloxane. The light source is typically a medium pressure mercury-arc lamp. The dose of radiation is typically from
30 to 1,000 mJ/cm^, alternatively from 50 to 500 mJ/cm^. Moreover, the silicone composition can be externally heated during or after exposure to radiation to enhance the rate and/or extent of cure.
[0078] When the curable silicone composition is a peroxide-curable silicone composition, the composition can be cured by exposing it to a temperature from RT to 180 °C, for a period from 0.05 to 1 h.
[0079] The method may also include the step(s) of disposing the transparent semiconductor on the polymer layer, the tie layer and/or the substrate. In this step or steps, the transparent semiconductor may also include the CGC disposed thereon such that this step may be a part of, or a further definition of, the step of disposing the polymer layer on the CGC. The transparent semiconductor can be disposed (e.g. applied) by any suitable mechanisms known in the art but is typically applied using an applicator in a continuous mode. Other suitable mechanisms of application include applying a force to the transparent semiconductor to more completely contact the transparent semiconductor and the polymer layer, the CGC, the tie layer and/or the substrate, either directly or indirectly. In one embodiment, the method includes the step of compressing the transparent semiconductor and the polymer layer, the CGC, the tie layer and/or the substrate. Compressing the transparent semiconductor and the polymer layer, the CGC, the tie layer and/or the substrate maximizes contact and maximize encapsulation, if desired. The step of compressing may be further defined as applying a vacuum to the transparent semiconductor and the polymer layer, the CGC, the tie layer and/or the substrate. Alternatively, a mechanical weight, press, or roller (e.g. a pinch roller) may be used for compression. Further, the step of compressing may be further defined as laminating. Still further, the method may include the step of applying heat to the module or any or all of the substrate, the CGC, the transparent semiconductor, polymer layer, and/or the tie layer. Heat may be applied in combination with any other step or may be applied in a discrete step. The entire method may be continuous or batch or may include a combination of continuous and batch steps.
[0080] The step of disposing the polymer layer may be further defined as encapsulating at least part of the transparent semiconductor and/or the CGC with the polymer layer. More specifically, the polymer layer may partially or totally encapsulate the transparent semiconductor and/or CGC. Alternatively, the polymer layer may not encapsulate the transparent semiconductor and/or CGC. Partial encapsulation encourages more efficient manufacturing. The polymer layer allows for production of a module with the optical and chemical advantages of silicone.
Additionally, use of silicone allows for formation of UV transparent tie layers and/or polymer layers and may increase cell efficiency by at least 1 to 5 relative . Use of peroxide catalysts, as described above, may also provide increased transparency and increased cure speeds. Sheets of the curable composition including silicone may be used for assembly of the module.
[0081 ] In yet another embodiment of this method, the polymer layer and/or the tie layer may be further defined as a film and the step of disposing may be further defined as applying the film, e.g. applying the film to the CGC. In this embodiment, the step of applying the film may be further defined as melting the film. Alternatively, the film may be laminated on the CGC.
[0082] In one embodiment, the method includes the step of laminating to melt the tie layer and/or the polymer layer. In an alternative embodiment, the method includes the step of applying the transparent semiconductor to a substrate by chemical vapor deposition. This step may be performed by any mechanisms known in the art. The method may also include the step of applying the additional tie layer, substrate, and/or superstrate.
[0083] This disclosure also provides additional embodiments of the module itself, independent from the aforementioned method. In one embodiment, the module includes the transparent semiconductor, the polymer layer, and the CGC disposed on the transparent semiconductor and sandwiched between the transparent semiconductor and the polymer layer. Various embodiments of the module itself are not limited by the aforementioned method steps. Accordingly, the CGC, relative to the module itself, may be formed by any method or process known in the art or the method described above. In various embodiments, the CGC is formed using electrical heating, hot filament processes, UV irradiation, IR irradiation, microwave irradiation, X-ray irradiation, electronic beams, laser beams, plasma, RF, radio frequency plasma enhanced chemical vapor deposition (RF-PECVD), electron-cyclotron-resonance plasma-enhanced chemical vapor deposition (ECR-PECVD), inductively coupled plasma enhanced chemical vapor deposition (ICP-ECVD), plasma beam source plasma enhanced chemical vapor deposition (PBS- PECVD), and/or combinations thereof.
Example 1:
[0084] In a first example, a CGC is deposited on glass slides, monocrystalline silicon wafers, monocrystalline Si/AIN structures and Sapphire/GaN structures in a parallel- plate capacitive type plasma reactors operating in dual frequency or reactive ion- etching (RIE) configurations at 50°C. Deposition processes are conducted by introducing a reactive gas mixture in a deposition chamber. The reactive gas mixture initially includes silicon and carbon containing precursors, such as trimethylsilane ((CH3)3SiH), and inert gas such as argon (Ar) for depositing the amorphous hydrogenated silicon carbide portion of the CGC structure. Further, an oxidizer such as oxygen (02) is added to the reactive gas mixture in the deposition chamber for depositing amorphous hydrogenated silicon oxycarbide (SiOC:H) portion of the CGC. In this way, the composition of the CGC is gradually-changed from hydrogenated oxygen-rich SiOC:H at the interface with polymer layer to hydrogenated oxygen deficient SiOC:H in the direction away from the polymer layer and further to hydrogen-rich amorphous SiC and still further to amorphous SiC with less hydrogen content at the opposite interface with the transparent semiconductor.
Example 2:
[0085] In a second example, the reactive gas mixture initially includes a silicon containing precursor, such as monosilane (SiH4), a carbon-containing precursor, such as ethylene (C2H4), hydrogen (H2), and an inert gas such as argon (Ar) for depositing the amorphous hydrogenated silicon carbide portion of the CGC structure. Further oxidizers such as nitrous oxide (N20) and oxygen (02) are added to the reactive gas mixture in the deposition chamber for depositing amorphous hydrogenated silicon oxy carbon nitride (SiOCN:H) portion of the CGC structure. In this way the CGC is gradually-changed from hydrogenated oxygen and nitrogen rich SiOCN:H at the interface with polymer layer to hydrogenated oxygen and nitrogen deficient SiOCN:H in the direction away from the polymer layer and further to hydrogen-rich SiC and still further to SiC with less hydrogen content at the opposite interface with the transparent semiconductor.
[0086] Compositional and optical properties of the CGC are changed within a single process run and without interrupting the plasma process. Fourier-transformed infrared (FTIR) spectra of different portions of the CGC are compared in Figure 2. More specifically, the FTIR is used to determine how the gradient of the CGC changes from hydrogenated silicon carbide (SiC:H) to hydrogenated silicon oxycarbonitride
(SiOCN:H). The FT-IR spectrometer is commercially available from, e.g. Thermo Fisher Scientific Inc. (Waltham, MA) under the trade name of Nexus. Compositional change of CGCs in depth is also analyzed by X-ray photoelectron spectroscopy (XPS) and shown in Figures 3A/B. More specifically, XPS spectra are taken by using an instrument from Kratos Analytical Ltd. (Chestnut Ridge, NY).
[0087] After formation, the examples are analyzed using a spectroscopic ellipsometer to determine refractive indices and deposition rate. The ellipsometer is commercially available from J.A. Wollam Co. Inc (Lincoln, NE). The composition, density and optical characteristics of the CGC are changed by varying low frequency (LF) power, while depositing in dual-frequency PECVD reactor configuration. Higher LF power increases ion energy which affects the intensity of ion bombardment. As a result, denser coatings with higher refractive index and absorption coefficient (passing through a maximum) are deposited slower by increasing the LF power, as can be seen in Figure 4.
Example 3:
[0088] In a third example, the composition and optical properties of various SiOC:H coatings are changed by varying the oxygen gas flow rate. For (CH3)3SiH-02-Ar chemistry, 02 flow rate typically changes optical properties and deposition rate of the CGC. In Figure 11 it is seen that higher 02 flow rate results in higher deposition rate (passing through a maximum), lower absorption coefficient and refractive index values. This is due to the gradual transition from hydrogenated SiC to hydrogenated SiOC or SiOCN expressed by changes in the FTIR Si-C, Si-0 and Si-N stretching oscillations as can be seen from the spectra in Figure 2. The range of refractive index change realized in the described graded layer is from 1.45 to 3.2.
Example 4:
[0089] In a fourth example, a PDMS solution, as the polymer layer, is disposed on a CGC followed by subsequent curing. Refractive index and thickness of the polymer layer are correspondingly 1.41 and 0.5 mm. In Figure 6, the minimized reflectance achieved by this structure from monosilane chemistry is set forth and is compared to uncoated Si wafers, similar wafers coated with only the PDMS encapsulant, and single antireflective coatings disposed on similar wafers. In Figure 7, a similar comparison is made for a CGC formed from trimethylsilane chemistry.
[0090] Light reflection and transmission are typically measured using a spectrophotometer such as a Cary 5000 UV-Vis-NIR spectrophotometer with integrated sphere commercially available from Agilent Technologies, Inc. In Figures 6 and 7, superior reduction in light reflection loss is provided by the CGCs of this disclosure as compared to bare Si wafer and the single antireflective coating. Figure 7 also shows that the light transmission spectrum of the CGC is approximately equal to that of the reference glass, except for the wavelength range below 400 nm due to light absorbance. A portion of this light absorption causes luminescence with a broad emission band from 375 to 675 nm, as it is seen from the CGC spectrum set forth in Figure 8. The broad emission band originates mainly from defects in the Si-O-C-H amorphous complex.
[0091] Figure 9 includes data that shows reduced Fresnel reflection loss for Si/AIN structures, as LEDs, that include the CGC of this disclosure. Minimized light reflection for these same structures is shown in Figure 10 for the particular wavelength range 420-480 nm.
[0092] Reduced light reflection and enhanced light transmission for CGC-coated Al203/GaN structures compared to uncoated are shown in Figures 11A/B. In Figures 12A/B and 13A/B reduced light reflection and improved light transmission are demonstrated for CGC and bi-layer CGC-polymer antireflective structures on A^C GaN substrates (as the transparent semiconductor) with CGC being deposited from trimethylsilane (Figure 12A/B) and monosilane (Figure 13A/B), respectively.
[0093] Figure 14 shows bi-layer CGC-polymer antireflective structure design relative to refractive index and thickness including a second order exponential model fit.
[0094] One or more of the values described above may vary by ± 5%, ± 10%, ± 15%, ± 20%, ± 25%, etc. so long as the variance remains within the scope of the disclosure. Unexpected results may be obtained from each member of a Markush group independent from all other members. Each member may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims. The subject matter of all combinations of independent and dependent claims, both singly and multiply dependent, is herein expressly contemplated. The disclosure is illustrative including words of description rather than of limitation. Many modifications and variations of the present disclosure are possible in light of the above teachings, and the disclosure may be practiced
otherwise than as specifically described herein. In various non-limiting embodiments, one or more compounds, components, method steps, etc. as set forth in PCT/US2010/049829, which is expressly incorporated herein by reference in its entirety, may be used in whole or in part with any one or more portions of the instant disclosure. The symbol "+" used herein describes that values may vary by "+" or "-" the number described after the "+" symbol.
Claims
1. A method of forming a light emitting diode module comprising:
a transparent semiconductor having a refractive index of 2.7 + 1.2;
a polymer layer that is disposed on the transparent semiconductor and that has a refractive index of 1.5 ± 0.1;
a compositional graded coating that is disposed on the transparent semiconductor and sandwiched between the transparent semiconductor and the polymer layer, that has a thickness and a refractive index varying along the thickness from a first refractive index from (2.2 + 0.5 to 3.3 + 0.4) at a first end to a second refractive index of 1.5 + 0.2 at a second end adjacent to the polymer layer, and that comprises a gradient comprising SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) along the thickness,
said method comprising;
A. continuously depositing the compositional graded coating on the transparent semiconductor using chemical vapor deposition, and subsequently
B. disposing the polymer layer on the compositional graded coating to form the light emitting diode.
2. The method of claim 1 wherein the transparent semiconductor is a top surface of a light emitting diode.
3. The method of claim 1 wherein the transparent semiconductor is chosen from A1203, GaN, and A1N.
4. The method of any one of claims 1 to 3 wherein the light emitting diode comprises Si:H disposed between the polymer layer and the transparent semiconductor.
5. The method of any one of claims 1 to 4 wherein the chemical vapor deposition is plasma-enhanced and optionally operates in a reactive-ion etching mode or a dual frequency mode.
6. The method of any one of claims 1 to 5 further comprising the step of depositing the Si:H as an intermediate layer disposed between the compositional graded coating and the transparent semiconductor such that the compositional graded coating has a refractive index varying along the thickness from the first refractive
index of 2.2 + 0.5 at the first end to the second refractive index of 1.45 + 0.05 at the second end adjacent to the polymer layer.
7. The method of claim 6 wherein the intermediate layer has a refractive index from 3.2 + 0.4.
8. The method of any one of claims 1 to 5 wherein the Si:H is present in the compositional graded coating such that the gradient comprises Si:H, SiC:H and SiOCN:H and the compositional graded coating has a refractive index varying along the thickness from the first refractive index of 3.3 + 0.4 at the first end to the second refractive index of 1.45 + 0.05 at the second end adjacent to the polymer layer.
9. The method of any preceding claim wherein the step of continuously depositing comprises introducing monosilane gas to the transparent semiconductor, introducing a hydrocarbon gas to the transparent semiconductor, and introducing at least one of nitrous oxide, oxygen, and carbon dioxide to the transparent semiconductor.
10. The method of claim 9 wherein the hydrocarbon gas comprises at least one of methane, ethylene, and acetylene.
11. The method of any preceding claim wherein the step of continuously depositing occurs at room temperature or occurs at a temperature above room temperature or at about 50°C in a reactive-ion etching or dual-frequency plasma mode.
12. The method of any preceding claim wherein the gradient comprises;
SiC:H and SiOCN:H;
SiC:H and SiOC:H;
SiC:H and Si:H; or
Si:H, SiC:H, SiOCN:H, and SiOC:H.
13. The method of any preceding claim wherein the polymer layer comprises a silicone.
14. The method of any preceding claim wherein the compositional graded coating has a thickness from 50 to 1000 nm and the polymer layer has a thickness of at least 50 μιη.
15. A light emitting diode module formed from the method set forth in any preceding claim.
16. A light emitting diode module comprising:
a transparent semiconductor having a refractive index of 2.7 + 1.2;
a polymer layer that is disposed on the transparent semiconductor and that has a refractive index of 1.5 ± 0.1 ; and
a compositional graded coating that is disposed on said transparent semiconductor and sandwiched between said transparent semiconductor and said polymer layer, that has a thickness and a refractive index varying along the thickness from a first refractive index from (2.2 + 0.5 to 3.3 + 0.4) at a first end to a second refractive index of 1.5 + 0.2 at a second end adjacent to the polymer layer, and that comprises a gradient comprising SiC:H and (SiOCN:H; SiOC:H; and/or Si:H) along the thickness.
17. The module of claim 16 wherein said transparent semiconductor is a light emitting diode or said transparent semiconductor is chosen from AI2O3, GaN, and A1N.
18. The module of claim 16 or 17 wherein said Si:H is present in an intermediate layer having a refractive index of 3.2 + 0.4 and disposed between said compositional graded coating and said transparent semiconductor such that said compositional graded coating has a refractive index varying along the thickness from the first refractive index of 2.2 + 0.5 at said first end to the second refractive index of 1.45 + 0.05 at said second end adjacent to said polymer layer.
19. The module of claim 16 or 17 wherein said Si:H is present in said compositional graded coating such that said gradient comprises Si:H, SiC:H and SiOCN:H and said compositional graded coating has a refractive index varying along the thickness from the first refractive index of 3.3 + 0.4 at said first end to the second refractive index of 1.45 + 0.05 at said second end adjacent to said polymer layer.
20. The module of any one of claims 16 to 19 wherein said gradient comprises;
SiC:H and SiOCN:H;
SiC:H and SiOC:H;
SiC:H and Si:H; or
Si:H, SiC:H, SiOCN:H, and SiOC:H.
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