CN108155562B - Preparation method of aluminum and phosphorus co-doped silicon nanocrystal - Google Patents
Preparation method of aluminum and phosphorus co-doped silicon nanocrystal Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 110
- 239000010703 silicon Substances 0.000 title claims abstract description 110
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 86
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 34
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 33
- 239000011574 phosphorus Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 66
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 238000002161 passivation Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 16
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims abstract description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 24
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 24
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 claims description 19
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 17
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 14
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 13
- 239000001272 nitrous oxide Substances 0.000 claims description 12
- 239000005922 Phosphane Substances 0.000 claims description 9
- 238000005191 phase separation Methods 0.000 claims description 9
- 229910000064 phosphane Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 53
- 239000010409 thin film Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910003915 SiCl2H2 Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/305—Structure or shape of the active region; Materials used for the active region characterised by the doping materials used in the laser structure
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Optics & Photonics (AREA)
- Luminescent Compositions (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Abstract
The invention provides a preparation method of aluminum and phosphorus co-doped silicon nanocrystals, which comprises the following steps: step 1), providing a substrate, and depositing an aluminum and phosphorus doped silicon dioxide film on the substrate by adopting a low-pressure chemical vapor deposition method; step 2), phase-splitting heat treatment technology is adopted to separate out aluminum and phosphorus doped silicon nanocrystals in the silicon dioxide film in a phase-splitting manner, and the silicon nanocrystals are embedded in the silicon dioxide film; and 3) carrying out hydrogen passivation treatment on the silicon dioxide film and the silicon nanocrystals to remove defects and dangling bonds in the silicon dioxide film and the silicon nanocrystals. The invention adopts aluminum and phosphorus to carry out P-type and N-type doping respectively, enlarges the luminous spectral range of the silicon nanocrystal, reduces photon absorption generated by Auger effect, improves the luminous efficiency of the silicon nanocrystal, simultaneously, the impurity doping amount of the prepared silicon nanocrystal is adjustable, the crystallization quality is good, and the silicon nanocrystal is an ideal light source on a silicon substrate.
Description
Technical Field
The invention belongs to the technical field of silicon photons, and particularly relates to a preparation method of an aluminum and phosphorus co-doped silicon nanocrystal for a silicon-based light source.
Background
With the rise of intelligent devices and the popularization of social networks, communication traffic is growing explosively. The traditional electrical interconnection technology faces the problems of overlarge power consumption and overhigh time delay due to the increase of the number of transistors and the multiple increase of the throughput of chips, and the electricity consumed by the current global computing center accounts for 0.8 percent of the total electricity generation. The development of silicon photon technology provides an effective way for solving the problems. On one hand, the manufacturing process of the silicon-based integrated optical device is completely compatible with the microelectronic process, and the light wave is an electromagnetic wave (200-; on the other hand, Wavelength Division Multiplexing (WDM) greatly improves the utilization rate of the communication bandwidth; in addition, optical communication has the advantages of small time delay, less heat generation, electromagnetic interference resistance and the like. Therefore, the silicon photonics technology is becoming the leading edge and hot spot of the information science technology, and developed countries including the united states, european union, japan, and the like are increasingly placing the silicon photonics technology in the strategic technical plan, and striving to dominate the new electronic information technology revolution.
2 3 2 5 2The main research fields of silicon photon technology are light source, electrooptical modulation, optical detection, optical multiplexing and waveguide fiber coupling technology, wherein a pure silicon-based light source is a difficulty of silicon photon technology, compared with the commonly used III-V group laser technology, the silicon-based light source has lower cost, small coupling loss of optical fiber and waveguide and high integration level, and is an ideal on-chip light source, but since bulk silicon is an indirect bandgap material, the pure silicon light source is very difficult to realize.
Disclosure of Invention
in view of the above disadvantages of the prior art, an object of the present invention is to provide a method for preparing an aluminum-phosphorus co-doped silicon nanocrystal, which is used to solve the problem that a silicon-based laser source in the prior art is difficult to implement.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing an aluminum and phosphorus co-doped silicon nanocrystal, comprising the steps of: step 1), providing a substrate, and depositing an aluminum and phosphorus doped silicon dioxide film on the substrate by adopting a low-pressure chemical vapor deposition method; step 2), phase-splitting heat treatment technology is adopted to separate out aluminum and phosphorus doped silicon nanocrystals in the silicon dioxide film in a phase-splitting manner, and the silicon nanocrystals are embedded in the silicon dioxide film; and 3) carrying out hydrogen passivation treatment on the silicon dioxide film and the silicon nanocrystals to remove defects and dangling bonds in the silicon dioxide film and the silicon nanocrystals.
As a preferred scheme of the preparation method of the aluminum and phosphorus co-doped silicon nanocrystal, the preparation method comprises the following steps:
Step 1), providing a monocrystalline silicon substrate, placing the monocrystalline silicon substrate into a vacuum chamber, vacuumizing, heating the substrate to 700-900 ℃, introducing dichlorosilane, phosphine, trimethylaluminum steam and nitrous oxide gas, and depositing an aluminum and phosphorus doped silicon dioxide film on the surface of the monocrystalline silicon substrate; the reaction in the vacuum chamber takes place as follows:
SiCl2H2+2N2O→SiO2+2N2↑+2HCl↑
2PH3+8N2O→P2O5+8N2↑+3H2O↑
2Al(CH3)3+24N2O→Al2O3+24N2↑+6CO2↑+9H2O↑
step 2), carrying out high-temperature phase splitting treatment on the deposited aluminum-phosphorus doped silicon dioxide film in a vacuum environment to separate out aluminum-phosphorus doped silicon nanocrystals in the silicon dioxide film in a phase-splitting manner, wherein the treatment temperature is 1100-1400 ℃, and the treatment time is 30-120 minutes; under the high temperature condition, silicon can be separated out from the silicon dioxide film to form silicon nanocrystals, the size of the silicon nanocrystal grains is influenced by the temperature and time of heat treatment, and meanwhile, Cl elements possibly existing in the film can be removed at high temperature, so that the quality of the film is improved.
And 3) passivating the silicon dioxide film and the silicon nanocrystals in a hydrogen atmosphere at the temperature of 400-600 ℃. The passivation treatment of the hydrogen is beneficial to reducing the defects and dangling bonds in the silicon dioxide film and the silicon nanocrystals, thereby improving the luminous efficiency of the silicon nanocrystals.
In practical application, the split-phase heat treatment and the hydrogen passivation treatment can be carried out in a chemical vapor deposition chamber, and the method comprises the following steps:
Step 1), providing a monocrystalline silicon substrate, placing the monocrystalline silicon substrate into a vacuum chamber, vacuumizing, heating the substrate to 700-900 ℃, introducing dichlorosilane, phosphine, trimethylaluminum steam and nitrous oxide gas, and depositing an aluminum and phosphorus doped silicon dioxide film on the surface of the monocrystalline silicon substrate; the reaction in the vacuum chamber takes place as follows:
SiCl2H2+2N2O→SiO2+2N2↑+2HCl↑
2PH3+8N2O→P2O5+8N2↑+3H2O↑
2Al(CH3)3+24N2O→Al2O3+24N2↑+6CO2↑+9H2O↑
Step 2), carrying out high-temperature phase splitting treatment on the deposited aluminum-phosphorus doped silicon dioxide film in a vacuum chamber to separate out aluminum-phosphorus doped silicon nanocrystals in the silicon dioxide film in a phase-splitting manner, wherein the treatment temperature is 1100-1400 ℃, and the treatment time is 30-120 minutes; under the high temperature condition, silicon can be separated out from the silicon dioxide film to form silicon nanocrystals, the size of the silicon nanocrystal grains is influenced by the temperature and time of heat treatment, and meanwhile, Cl elements possibly existing in the film can be removed at high temperature, so that the quality of the film is improved.
And 3) reducing the temperature of the monocrystalline silicon substrate to 400-600 ℃, and introducing hydrogen into the vacuum chamber to passivate the silicon dioxide film and the silicon nanocrystals. The passivation treatment of the hydrogen is beneficial to reducing the defects and dangling bonds in the silicon dioxide film and the silicon nanocrystals, thereby improving the luminous efficiency of the silicon nanocrystals.
Preferably, the pressure in the vacuum chamber after step 1) evacuation is no greater than 5 x 10 -2 pa.
preferably, in step 1), the ratio of dichlorosilane, phosphane, trimethylaluminum vapor and nitrous oxide gas is SiCl 2 H 2: PH 3: Al (CH 3): N 2 O ═ 15-25:1.5-2.5:1: 70-90.
Preferably, in the step 1), the deposition time of the silicon dioxide film is 3-10 minutes.
Preferably, in the step 2), the temperature of the phase separation heat treatment is 1150-1250 ℃.
Preferably, in the step 2), the time of the phase separation heat treatment is 30-120 minutes.
Preferably, in the step 3), the temperature of the passivation treatment is 450-550 ℃ and the time is not less than 40 minutes.
Preferably, in the step 3), the time of the passivation treatment is 40-100 minutes.
As described above, the preparation method of the aluminum and phosphorus co-doped silicon nanocrystal of the invention has the following beneficial effects:
The invention adopts aluminum and phosphorus to carry out P-type and N-type doping respectively, enlarges the luminous spectral range of the silicon nanocrystal, reduces photon absorption generated by Auger effect, improves the luminous efficiency of the silicon nanocrystal, simultaneously, the impurity doping amount of the prepared silicon nanocrystal is adjustable, the crystallization quality is good, and the silicon nanocrystal is an ideal light source on a silicon substrate.
Drawings
Fig. 1 is a schematic flow chart showing the steps of the preparation method of aluminum and phosphorus co-doped silicon nanocrystals of the present invention.
Fig. 2 to 5 show structural diagrams of the steps of the preparation method of the aluminum-phosphorus co-doped silicon nanocrystal of the invention.
Description of the element reference numerals
101 single crystal silicon substrate
102 silicon dioxide film
103 silicon nanocrystals
104 hanging key
S11-S13 steps 1) -3)
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 5. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the drawings only show the components related to the present invention rather than being drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of each component in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
Example 1
As shown in fig. 1 to 5, the present embodiment provides a method for preparing an aluminum and phosphorus co-doped silicon nanocrystal 103, including the steps of: step 1) S11, providing a substrate, and depositing an aluminum and phosphorus doped silicon dioxide film 102 on the substrate by using a low-pressure chemical vapor deposition method; step 2) S12, phase-splitting aluminum and phosphorus doped silicon nanocrystals 103 in the silicon dioxide film 102 by adopting a phase-splitting heat treatment process, wherein the silicon nanocrystals 103 are embedded in the silicon dioxide film 102; step 3) S13, performing hydrogen passivation treatment on the silicon dioxide film 102 and the silicon nanocrystals 103 to remove defects and dangling bonds 104 in the silicon dioxide film 102 and the silicon nanocrystals 103.
Specifically, the preparation method of the aluminum and phosphorus co-doped silicon nanocrystal 103 comprises the following steps:
As shown in fig. 1 and fig. 2 to fig. 3, step 1) providing a monocrystalline silicon substrate 101, placing the monocrystalline silicon substrate 101 into a vacuum chamber, vacuumizing, heating the substrate to 700 to 900 ℃, introducing dichlorosilane, phosphane, trimethylaluminum vapor and nitrous oxide gas, and depositing an aluminum and phosphorus doped silicon dioxide film 102 on the surface of the monocrystalline silicon substrate 101; the reaction in the vacuum chamber takes place as follows:
SiCl2H2+2N2O→SiO2+2N2↑+2HCl↑
2PH3+8N2O→P2O5+8N2↑+3H2O↑
2Al(CH3)3+24N2O→Al2O3+24N2↑+6CO2↑+9H2O↑
For example, the pressure in the vacuum chamber after the step 1) is vacuumized is not more than 5 × 10 -2 pa, the ratio of the dichlorosilane, the phosphane, the trimethylaluminum vapor and the nitrous oxide gas is SiCl 2 H 2, PH 3: Al (CH 3): N 2 O ═ 15-25:1.5-2.5:1:70-90, and the deposition time of the silicon dioxide film 102 is 3-10 minutes.
as shown in fig. 1 and 4, then, performing step 2), performing high-temperature phase splitting treatment on the deposited aluminum-phosphorus doped silicon dioxide thin film 102 in a vacuum environment to separate out aluminum-phosphorus doped silicon nanocrystals 103 in the silicon dioxide thin film 102 in a phase separation manner, wherein the treatment temperature is 1100-1400 ℃, and the treatment time is 30-120 minutes; under the high temperature condition, silicon can be separated out from the silicon dioxide film 102 to form the silicon nanocrystalline 103, the size of the silicon nanocrystalline 103 grains is influenced by the temperature and the time of heat treatment, and the Cl element possibly existing in the film can be removed at the high temperature, so that the quality of the film is improved.
As an example, in the step 2), the temperature of the phase separation heat treatment is 1150-1250 ℃, and the time of the phase separation heat treatment is 30-120 minutes.
As shown in fig. 1 and 5, step 3) is finally performed to passivate the silicon dioxide film 102 and the silicon nanocrystals 103 in a hydrogen atmosphere at a temperature of 400 to 600 ℃. The passivation treatment of hydrogen is beneficial to reducing defects and dangling bonds 104 in the silicon dioxide film 102 and the silicon nanocrystals 103, thereby improving the luminous efficiency of the silicon nanocrystals 103.
For example, in step 3), the temperature of the passivation treatment is 450 to 550 ℃, and the time is not less than 40 minutes, and in this embodiment, the time of the passivation treatment is 40 to 100 minutes.
In this embodiment, step 1), step 2), step 3) may be performed in different chambers.
Example 2
As shown in fig. 1 to 5, this embodiment provides a method for preparing an aluminum and phosphorus co-doped silicon nanocrystal 103, in practical application, both phase-splitting heat treatment and hydrogen passivation treatment can be performed in a chemical vapor deposition chamber, and the preparation method includes the following steps:
As shown in fig. 1 and fig. 2 to fig. 3, step 1) providing a monocrystalline silicon substrate 101, placing the monocrystalline silicon substrate 101 into a vacuum chamber, vacuumizing, heating the substrate to 700 to 900 ℃, introducing dichlorosilane, phosphane, trimethylaluminum vapor and nitrous oxide gas, and depositing an aluminum and phosphorus doped silicon dioxide film 102 on the surface of the monocrystalline silicon substrate 101; the reaction in the vacuum chamber takes place as follows:
SiCl2H2+2N2O→SiO2+2N2↑+2HCl↑
2PH3+8N2O→P2O5+8N2↑+3H2O↑
2Al(CH3)3+24N2O→Al2O3+24N2↑+6CO2↑+9H2O↑
As shown in fig. 1 and 4, step 2), performing high-temperature phase-splitting treatment on the deposited aluminum-phosphorus doped silicon dioxide film 102 in a vacuum chamber to separate out aluminum-phosphorus doped silicon nanocrystals 103 from the silicon dioxide film 102 in a phase-separated manner, wherein the treatment temperature is 1100-1400 ℃, and the treatment time is 30-120 minutes; under the high temperature condition, silicon can be separated out from the silicon dioxide film 102 to form the silicon nanocrystalline 103, the size of the silicon nanocrystalline 103 grains is influenced by the temperature and the time of heat treatment, and the Cl element possibly existing in the film can be removed at the high temperature, so that the quality of the film is improved.
as shown in fig. 1 and 5, in step 3), the temperature of the monocrystalline silicon substrate 101 is reduced to 400 to 600 ℃, and hydrogen is introduced into the vacuum chamber to passivate the silicon dioxide film 102 and the silicon nanocrystals 103. The passivation treatment of hydrogen is beneficial to reducing defects and dangling bonds 104 in the silicon dioxide film 102 and the silicon nanocrystals 103, thereby improving the luminous efficiency of the silicon nanocrystals 103.
The method comprises the steps of selecting dichlorosilane, phosphane, trimethylaluminum and nitrous oxide as reactants of a chemical vapor deposition silicon dioxide film 102, wherein the trimethylaluminum can be placed in an evaporation tank at about 100 ℃ to evaporate, or can be carried out by using carrier gas such as Ar, H 2 and N 2, before the silicon dioxide film 102 enters a reaction chamber, the dichlorosilane, the phosphane and the trimethylaluminum are mixed and then are introduced into the reaction chamber together, wherein in order to ensure complete reaction, the substrate temperature is kept at 700-900 ℃, according to the flow of input gas, the growth rate of the silicon dioxide film 102 can be 50-150 nm/min, the overall thickness of the film is preferably no more than 500nm, after the film deposition is finished, high-temperature heat treatment can be carried out in situ in a vacuum chamber for chemical vapor deposition, gas introduction is stopped, vacuumizing is carried out to less than 5 × 10 -2 pa, the substrate temperature is raised to 1100-1400 ℃, the silicon single crystal can be separated out in phase by using the silicon dioxide film 102 at the slow temperature, the silicon nano-crystal 103 is formed in the silicon dioxide film 102, the temperature and the silicon nano crystal passivation temperature is reduced by about 10 nm, the nano crystal passivation time when the silicon dioxide film is subjected to the hydrogen gas phase passivation, the silicon dioxide film passivation, the silicon nano crystal passivation temperature is reduced by about 10 nano crystal passivation, the silicon nano crystal passivation temperature is reduced by about 10 nano crystal passivation time is reduced by reducing the silicon nano crystal passivation time of the silicon thin film 102, the silicon thin film passivation process under the hydrogen, the silicon nano crystal passivation time of the silicon nano crystal passivation process.
In a specific implementation process, a specific flow of the preparation method of the aluminum-phosphorus co-doped silicon nanocrystal 103 of this embodiment is as follows:
Step 1), preparing a SiO 2 thin film by CVD, namely cleaning a monocrystalline silicon substrate 101 by absolute ethyl alcohol, hydrofluoric acid and water, drying the substrate by blowing, putting the substrate into a vacuum chamber, vacuumizing the vacuum chamber to 2 x 10 -2 pa, heating the substrate to 850 ℃, introducing dichlorosilane, phosphane, trimethylaluminum steam and nitrous oxide gas, wherein the flow ratio of the gases is SiCl 2 H 2, PH 3, Al (CH 3) 3, N 2 O is 20:2:1:80, and the deposition time of the thin film is 5 minutes.
Step 2), phase-splitting heat treatment, namely stopping introducing various gases, pumping the vacuum chamber to 2 multiplied by 10 -2 pa, raising the temperature of the substrate to 1200 ℃, and then keeping for 60 minutes, wherein the size and the direction of the obtained silicon nanocrystals 103 are not necessarily consistent and are dispersed in the silicon dioxide film 102.
Step 3), hydrogen passivation treatment: the substrate temperature was lowered to 500 deg.C at 5 deg.C/min, hydrogen gas was introduced into the vacuum chamber at a flow rate of 100sccm for 60 minutes, and the dangling bond 104 was removed.
To further illustrate the advantages of the preparation method of the present invention, this example also provides a comparative example comprising the steps of:
Step 1), preparing a SiO 2 thin film by CVD, namely cleaning a monocrystalline silicon substrate 101 by absolute ethyl alcohol, hydrofluoric acid and water, drying the substrate by blowing, putting the substrate into a vacuum chamber, vacuumizing the vacuum chamber to 2 x 10 -2 pa, heating the substrate to 850 ℃, introducing dichlorosilane, phosphane, trimethylaluminum steam and nitrous oxide gas, wherein the flow ratio of the gases is SiCl 2 H 2, PH 3, Al (CH 3) 3, N 2 O is 20:2:1:80, and the deposition time of the thin film is 5 minutes.
Step 2), phase separation heat treatment, namely stopping introducing various gases, pumping the vacuum chamber to 2 x 10 -2 pa, raising the temperature of the substrate to 900 ℃, and then keeping the temperature for 60 minutes.
Step 3), hydrogen passivation treatment: the substrate temperature was lowered to 500 ℃ at a rate of 5 ℃/min, and hydrogen gas was introduced into the vacuum chamber at a flow rate of 100sccm for 60 minutes.
among them, the comparative example is different from the examples of the present application in that the temperature of the phase separation heat treatment is low, only 900 ℃, and the silicon nanocrystals 103 can be generated at this temperature, but the photoluminescence intensity is low, which is less than half of that of the samples obtained in the above examples.
as described above, the preparation method of the aluminum and phosphorus co-doped silicon nanocrystal 103 of the present invention has the following beneficial effects: the invention adopts aluminum and phosphorus to carry out P-type and N-type doping respectively, enlarges the luminous spectral range of the silicon nanocrystal 103, reduces photon absorption generated by Auger effect, improves the luminous efficiency of the silicon nanocrystal 103, simultaneously, the prepared silicon nanocrystal 103 has adjustable impurity doping amount and good crystallization quality, and is an ideal light source on a silicon substrate. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of aluminum and phosphorus co-doped silicon nanocrystals is characterized by comprising the following steps:
Step 1), providing a substrate, placing the substrate into a vacuum chamber, vacuumizing, and depositing an aluminum and phosphorus doped silicon dioxide film on the substrate by adopting a low-pressure chemical vapor deposition method;
Step 2), adopting a phase-splitting heat treatment process to separate aluminum and phosphorus-doped silicon nanocrystals in the silicon dioxide film in a phase-splitting manner, wherein the treatment temperature of the phase-splitting heat treatment process is 1100-1400 ℃;
And 3) carrying out hydrogen passivation treatment on the silicon dioxide film and the silicon nanocrystals.
2. the method for preparing aluminum and phosphorus co-doped silicon nanocrystals according to claim 1, comprising the steps of:
Step 1), providing a monocrystalline silicon substrate, placing the monocrystalline silicon substrate into a vacuum chamber, vacuumizing, heating the substrate to 700-900 ℃, introducing dichlorosilane, phosphine, trimethylaluminum steam and nitrous oxide gas, and depositing an aluminum and phosphorus doped silicon dioxide film on the surface of the monocrystalline silicon substrate;
Step 2), carrying out high-temperature phase splitting treatment on the deposited aluminum-phosphorus doped silicon dioxide film in a vacuum environment to separate out aluminum-phosphorus doped silicon nanocrystals in the silicon dioxide film in a phase-splitting manner, wherein the treatment temperature is 1100-1400 ℃, and the treatment time is 30-120 minutes;
And 3) passivating the silicon dioxide film and the silicon nanocrystals in a hydrogen atmosphere at the temperature of 400-600 ℃.
3. the method for preparing aluminum and phosphorus co-doped silicon nanocrystals according to claim 1, comprising the steps of:
step 1), providing a monocrystalline silicon substrate, placing the monocrystalline silicon substrate into a vacuum chamber, vacuumizing, heating the substrate to 700-900 ℃, introducing dichlorosilane, phosphine, trimethylaluminum steam and nitrous oxide gas, and depositing an aluminum and phosphorus doped silicon dioxide film on the surface of the monocrystalline silicon substrate;
step 2), carrying out high-temperature phase splitting treatment on the deposited aluminum-phosphorus doped silicon dioxide film in a vacuum chamber to separate out aluminum-phosphorus doped silicon nanocrystals in the silicon dioxide film in a phase-splitting manner, wherein the treatment temperature is 1100-1400 ℃, and the treatment time is 30-120 minutes;
and 3) reducing the temperature of the monocrystalline silicon substrate to 400-600 ℃, and introducing hydrogen into the vacuum chamber to passivate the silicon dioxide film and the silicon nanocrystals.
4. The method for preparing aluminum and phosphorus co-doped silicon nanocrystals according to claim 2 or 3, wherein the pressure in the vacuum chamber after the step 1) of evacuating is not more than 5 x 10 -2 pa.
5. The method of claim 2 or 3, wherein the ratio of dichlorosilane, phosphane, trimethylaluminum vapor and nitrous oxide gas in step 1) is SiCl 2 H 2, PH 3, Al (CH 3), N 2 O (15-25: 1.5-2.5:1: 70-90.
6. The method for preparing aluminum-phosphorus co-doped silicon nanocrystals according to claim 2 or 3, wherein: in the step 1), the deposition time of the silicon dioxide film is 3-10 minutes.
7. The method for preparing aluminum-phosphorus co-doped silicon nanocrystals according to claim 2 or 3, wherein: in the step 2), the temperature of the phase separation heat treatment is 1150-1250 ℃.
8. The method for preparing aluminum-phosphorus co-doped silicon nanocrystals according to claim 2 or 3, wherein: in the step 2), the time of the phase separation heat treatment is 30-120 minutes.
9. The method for preparing aluminum-phosphorus co-doped silicon nanocrystals according to claim 2 or 3, wherein: in the step 3), the temperature of the passivation treatment is 450-550 ℃, and the time is not less than 40 minutes.
10. The method for preparing aluminum and phosphorus co-doped silicon nanocrystal according to claim 9, wherein the method comprises the following steps: in the step 3), the time of passivation is 40-100 minutes.
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