CN105675442A - Method for measuring viscosity of substrate support polymer film - Google Patents
Method for measuring viscosity of substrate support polymer film Download PDFInfo
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- CN105675442A CN105675442A CN201610053675.1A CN201610053675A CN105675442A CN 105675442 A CN105675442 A CN 105675442A CN 201610053675 A CN201610053675 A CN 201610053675A CN 105675442 A CN105675442 A CN 105675442A
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- G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention provides a method for measuring viscosity of a substrate support polymer film. Firstly, the substrate support polymer film is heated and maintained at the constant temperature; then, a test liquid is placed on the surface of the polymer film maintained at the constant temperature to form liquid drops, the standing time is recorded, the polymer film is cooled, the liquid drops on the surface of the polymer film are removed, a wetting ridge is formed in the polymer/liquid drop/air three-phase lines on the polymer film without the liquid drops, and the height of the wetting ridge is measured; when the standing time of the liquid drops on the surface of the polymer film is longer than the relaxation time of the polymer film, the liquid drop standing time has a linear relation with the height of the wetting ridge, and the viscosity of the polymer film can be calculated according to the slope of the linear relation. By means of the measuring method provided by the invention, the viscosity of the substrate support polymer film can be accurately measured, the operation method is simple, the cost is low and the adaptability is wide.
Description
Technical field
The present invention relates to field of measuring technique, in particular to the measuring method of a kind of substrate support polymer thin film viscosity.
Background technology
The rheological property of polymkeric substance is the important foundation instructing polymer materials forming process. Viscosity (η) is an extremely important physical parameter of amorphous polymer, reflects polymer melt or the glutinous ability playing state polymer generation viscous fluid flow. The mechanical property of viscosity and material, thermotolerance, shaping and processing characteristics and work-ing life are closely related. Such as, reduce viscosity and can improve the processing fluidity of polymkeric substance, mold filling process polymer melt is easy to flow through narrow pipeline, it is to increase quality of item, also reduces injection moulding machine, forcing machine running institute energy requirement; High viscosity polymer goods are heated and deformation not easily occur, and have higher thermostability. Meanwhile, viscosity is the embodiment of macromolecular chain motion. Study Polymer Melts viscosity also has extremely important theory significance for the physical image of the structural models and molecular motion thereof that build polymkeric substance condensed state system.
Polymeric film is widely used in field of nanometer material technology. Using polymeric film as carrier, utilize various micro-nanofabrication technique, in the various nano-patterning structure of polymeric film surface preparation, and then the nano-functional material such as organic photoelectrical material, microelectronic device can be prepared. In addition, polymeric film also can directly be used as coated material and be applied to the fields such as packaged material, is possible not only to protection primer and corrodes from outside atmosphere, also can change the rub resistance of material, the hydrophobic or surface property such as oleophobic property, cohesiveness. What polymer thin film viscosity determined polymer nano material prepares processing conditions and use properties.
When polymer film thickness is reduced to below several hundred nanometers, the physicochemical property of polymeric film start to deviate with its bulk properties. Thickness is more low, and the degree of deviation is more big. The viscosity of polymer ultra-thin film also changes along with the reduction of film thickness, and such as, when temperature is 340K, 9nm polystyrene film ratio of viscosities body value reduces about three orders of magnitude.The viscosity of polymeric film is the function of film thickness, and the film of different thickness has different viscositys. In addition, interaction between primer and polymeric film also will affect the k value of film. Research finds, the viscosity of the polystyrene film in the upper polystyrene film ratio of viscosities silicon oxide substrate of the silicon base (H-Si) of surface passivation increases 3 times. When primer and polymeric film have relatively strong interaction time, the viscosity of film will reduce with thickness and increase. Thus, can not simply the viscosity of polymer body be equal to the viscosity of polymeric film.
Due to the method (such as rheometer) of traditional measurement mass polymer viscosity and rheological property and be not suitable for the research of nanometer-scale polymer film viscosity, between nearest more than ten years, researcher is devoted to develop the new measuring method of polymer thin film viscosity always, the viscosity measuring polymeric film as developed by Study Polymer Melts surface topography, by the viscosity of " nanometer Bubbling method (nano-bubbleinflation) " Study Polymer Melts film, the thickness dependence of glycerine surface polystyrene film " wetting removal " dynamics research film viscosity is swum in by research. but, the viscosity of the current Measurement accuracy polymeric film particularly polymeric film of substrate support is still that the one of educational circles challenges greatly.
Summary of the invention
It is an object of the invention to provide the measuring method of a kind of substrate support polymer thin film viscosity, it is possible to accurately measure the viscosity of substrate support polymeric film.
The technical scheme of the present invention is as follows:
The present invention provides the measuring method of a kind of substrate support polymer thin film viscosity, comprises the following steps:
(1) by the heating of substrate support polymeric film, also holding temperature is constant;
(2) test liquid is placed in the polymeric film surface that step (1) described holding temperature is constant, form drop, measure the contact angle θ value that described drop is formed on described polymeric film surface, the storage period t of record drop on polymeric film surface;
(3) polymeric film described in step (2) is cooled, remove the drop on described polymeric film surface, polymkeric substance/drop on the polymeric film surface of described removing drop/air triple-phase line place forms wetting ridge, measures the height h of wetting ridge;
(4) change the storage period t of drop on polymeric film surface, obtain the h～t variation relation of height h with drop t storage period of wetting ridge;
When described drop is when being greater than polymeric film time of relaxation the storage period on polymeric film surface, between the height of described drop storage period and described wetting ridge, there is the linear relationship shown in formula I;
Based on the slope k of formula I linear relationship, calculate the viscosity of polymeric film according to described formula II:
H=kt+b formula I,
Wherein, the height of the wetting ridge of h,
T drop in the storage period on polymeric film surface,
K slope,
B intercept;
η=0.37 γ sin θ/k formula II,
Wherein, the viscosity of η polymeric film,
The surface tension of γ drop,
The contact angle that θ drop and polymeric film surface are formed,
Slope in k formula I.
Preferably, described in step (1), the thickness of polymeric film is 10～1000nm.
Preferably, described in step (1), the thickness of polymeric film is 50～500nm.
Preferably, in polymeric film described in step (1), polymkeric substance is linear polymer.
Preferably, described linear polymer comprises the blend of one or more in polystyrene, polystyrene derivative, methacrylate based polymers, polyvinyl tertbutyl ether, polyacrylonitrile, polymethacrylonitrile, polyvinyl acetate (PVA), polyphenylene oxide, polyvinyl chloride, polyvinylidene dichloride, vinyl fluoride base polymer, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, poly(lactic acid), nylon, polyhutadiene, polyisoprene, polysulfones, polyethers, or several multipolymers.
Preferably, the temperature of heating described in step (1) is higher than the second-order transition temperature of polymkeric substance.
Preferably, test liquid described in step (2) comprises glycerine, ethylene glycol, polyoxyethylene glycol oligopolymer, polyethylene oxide oligopolymer, dimethyl sulfoxide (DMSO), N, dinethylformamide or ionic liquid.
Preferably, described ionic liquid comprises 1-ethyl-3-methyl imidazolium tetrafluoroborate, 1-own base-3-methyl imidazolium tetrafluoroborate, 1-butyl-3 Methylimidazole trifluoromethyl sulfonic acid or 1-butyl-3 Methylimidazole Methylsulfate.
Preferably, described in step (2), the diameter of drop is 2～7mm.
Preferably, cooling described in step (3) adopts heat-eliminating medium that described polymeric film is cooled to room temperature;
Described heat-eliminating medium comprises ice bag, liquid nitrogen, dry ice or low-temperature metal plate.
The present invention provides the measuring method of a kind of substrate support polymer thin film viscosity, and first by the heating of substrate support polymeric film, also holding temperature is constant; Then test liquid is placed in the polymeric film surface that described holding temperature is constant, forms drop, and record storage period; Being cooled by polymeric film, remove the drop on polymeric film surface, the polymkeric substance/drop on the polymeric film surface of described removing drop/air triple-phase line place forms wetting ridge, measures the height of wetting ridge; Change drop storage period, obtain the variation relation of wetting ridge height with drop storage period, when described drop is when being greater than polymeric film time of relaxation the storage period on polymeric film surface, between described drop storage period and described wetting ridge height, there is linear relationship, the viscosity of polymeric film can be calculated according to the slope of its linear relationship. Measuring method provided by the invention can measure substrate support polymer thin film viscosity accurately, and working method is simple, cost is low, wide adaptability.
Accompanying drawing explanation
Fig. 1 is the shape appearance figure of the wetting ridge of PS film surface in the embodiment of the present invention 1;
Fig. 2 is the cross-sectional view of the wetting ridge shape looks of PS film surface in the embodiment of the present invention 1;
Fig. 3 is the cross-sectional view of the wetting ridge shape looks of PS film surface under different drop storage period in the embodiment of the present invention 1;
Fig. 4 is the height of the wetting ridge of PS film surface in the embodiment of the present invention 1 and h～t graph of a relation of drop storage period;
Fig. 5 is the height of the wetting ridge of PS film surface in the embodiment of the present invention 2 and h～t graph of a relation of drop storage period;
Fig. 6 is the height of the wetting ridge of PS film surface in the embodiment of the present invention 3 and h～t graph of a relation of drop storage period;
Fig. 7 be utilize that measuring method of the present invention records PS film viscosity and literature value in the embodiment of the present invention 3 compare figure;
Fig. 8 is the height of the wetting ridge of PS film surface in the embodiment of the present invention 4 and h～t graph of a relation of drop storage period;
Fig. 9 is the height of the wetting ridge of PS film surface in the embodiment of the present invention 5 and h～t graph of a relation of drop storage period;
Figure 10 is the height of the wetting ridge of PS film surface in the embodiment of the present invention 6 and h～t graph of a relation of drop storage period;
Figure 11 is the PS film viscosity of different base in the embodiment of the present invention 7 and the graph of a relation of PS film thickness.
Embodiment
The present invention provides the measuring method of a kind of substrate support polymer thin film viscosity, comprises the following steps:
(1) by the heating of substrate support polymeric film, also holding temperature is constant;
(2) test liquid is placed in the polymeric film surface that step (1) described holding temperature is constant, form drop, measuring the contact angle θ value that described drop is formed on described polymeric film surface, record drop is at polymeric film surface t storage period;
(3) polymeric film described in step (2) is cooled, remove the drop on described polymeric film surface, polymkeric substance/drop on the polymeric film surface of described removing drop/air triple-phase line place forms wetting ridge, measures the height h of wetting ridge;
(4) change the storage period t of drop on polymeric film surface, obtain the h～t variation relation of height h with drop t storage period of wetting ridge;
When described drop is when being greater than polymeric film time of relaxation the storage period on polymeric film surface, between the height of described drop storage period and described wetting ridge, there is the linear relationship shown in formula I;
Based on the slope k of formula I linear relationship, calculate the viscosity of polymeric film according to described formula II:
H=kt+b formula I,
Wherein, the height of the wetting ridge of h,
T drop in the storage period on polymeric film surface,
K slope,
B intercept;
η=0.37 γ sin θ/k formula II,
Wherein, the viscosity of η polymeric film,
The surface tension of γ drop,
The contact angle that θ drop and polymeric film surface are formed,
Slope in k formula I.
The present invention does not have special restriction for determination object, adopts substrate support polymeric film well known to those skilled in the art. In the present invention, the thickness of described polymeric film is preferably 10～1000nm, it is more preferable to be 50～500nm.
In the present invention, in described polymeric film, polymkeric substance is preferably linear polymer. In the present invention, described linear polymer preferably includes the blend of one or more in polystyrene and derivative, methacrylate based polymers, polyvinyl tertbutyl ether, polyacrylonitrile, polymethacrylonitrile, polyvinyl acetate (PVA), polyphenylene oxide, polyvinyl chloride, polyvinylidene dichloride, vinyl fluoride base polymer, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, poly(lactic acid), nylon, polyhutadiene, polyisoprene, polysulfones, polyethers, or several multipolymers.
The present invention preferably prepares smooth polymeric film in substrate, obtains substrate support polymeric film. In the present invention, described substrate not with described polymkeric substance generation chemical reaction, be only physical bond. In the present invention, described substrate preferably adopts surfacing, is easy to the material of heat transfer. In the present invention, the material of described substrate preferably includes sheet glass, silicon chip, sapphire, mica, iron, copper or aluminium.
The present invention does not have special restriction for the preparation method of described smooth polymeric film, adopts the technical scheme preparing polymeric film well known to those skilled in the art. In the present invention, the method preparing described smooth polymeric film preferably includes casting method, spin-coating method or dip coating.
The present invention is not particularly limited for substrate support polymeric film heats also constant the adopted mode of holding temperature, adopts well known to those skilled in the art for heating the technical scheme that also holding temperature is constant. The present invention preferably adopts precise temperature control thermal station, and to the heating of described substrate support polymeric film and holding temperature is constant. In the present invention, the temperature-controlled precision of described precise temperature control thermal station is preferably ± 1 DEG C. In the present invention, the temperature of described heating is preferably higher than the second-order transition temperature of polymkeric substance.
Complete the heating of substrate support polymeric film and holding temperature constant after, test liquid is placed in the constant polymeric film surface of described holding temperature by the present invention, forms drop, and records t storage period.In the present invention, described test liquid preferably meets following three conditions:
A () has lower rate of volatilization, owing to liquid volatilization is caused liquid-drop contact angle decreasing value to be less than 5 ° in measuring process;
B () has higher surface tension, form, on described polymeric film surface, the contact angle being greater than 30 °;
C () is incompatible with described polymkeric substance thermodynamics, in measuring process, test liquid can not permeate into polymkeric substance inside, polymkeric substance can not be produced plasticization effect.
In the present invention, described test liquid preferably includes glycerine, ethylene glycol, polyoxyethylene glycol oligopolymer, polyethylene oxide oligopolymer, dimethyl sulfoxide (DMSO), N, dinethylformamide or ionic liquid; Described ionic liquid preferably includes 1-ethyl-3-methyl imidazolium tetrafluoroborate, 1-own base-3-methyl imidazolium tetrafluoroborate, 1-butyl-3 Methylimidazole trifluoromethyl sulfonic acid or 1-butyl-3 Methylimidazole Methylsulfate.
Droplet dia size can affect the tolerance range of measuring result, and in the present invention, the diameter of described drop is preferably 2～7mm. In an embodiment of the present invention, the DSA10-MK2 type contact angle tester utilizing Kruss company of Germany to produce obtains the diameter of described drop.
The present invention does not have special restriction for the method for the contact angle θ value measuring described drop and the formation of described polymeric film surface, adopts the technical scheme of the contact angle θ value of the described drop of mensuration well known to those skilled in the art and the formation of described polymeric film surface. The present invention preferably adopts standardized equipment to measure described drop and the contact angle θ value of described polymeric film surface formation. In an embodiment of the present invention, the DSA10-MK2 type Drop Shape Analyzer adopting Kruss company of Germany to produce measures described drop and the contact angle θ value of described polymeric film surface formation.
The present invention by described drop after the constant polymeric film surface storage period t of described holding temperature, described polymeric film is cooled, remove the drop on described polymeric film surface, polymkeric substance/the drop on the polymeric film surface of described removing drop/air triple-phase line place forms wetting ridge, measures the height h of wetting ridge. In the present invention, described cooling preferably adopts heat-eliminating medium that described polymeric film is cooled to room temperature; Described heat-eliminating medium preferably includes ice bag, dry ice, liquid nitrogen or low-temperature metal plate. In the present invention, it may also be useful to heat-eliminating medium can realize cooling described polymeric film fast, to ensure the accuracy of measuring result.
In the present invention, after being cooled by described polymeric film, remove the drop on described polymeric film surface. The present invention does not have special restriction for the method for the drop on described removing polymeric film surface, adopts the technical scheme of the drop on removing polymeric film surface well known to those skilled in the art. The present invention preferably adopts filter paper to be exhausted by the drop on polymeric film surface.
In the present invention, after removing the drop on described polymeric film surface, the polymkeric substance/drop on the polymeric film surface of described removing drop/air triple-phase line place forms wetting ridge, measures the height h of wetting ridge. Due to the effect of drop surface tension vertical component, polymkeric substance/drop on described polymeric film surface/air triple-phase line place produces to be highly the projection deformation of tens nanometer to the ridge shape of several microns, described deformation is called wetting ridge, English wettingridge by name.The present invention does not have special restriction for the method for the height h of the wetting ridge of described measurement, adopts the technical scheme of the height h of the wetting ridge of measurement well known to those skilled in the art. The polymeric film removing drop is preferably positioned on atomic force microscope (AFM) test platform by the present invention, utilize AFM to record the shape appearance figure of wetting ridge on polymeric film surface and the cross-sectional view of wetting ridge shape looks of described removing drop, from the cross-sectional view of wetting ridge shape looks, obtain the height h of wetting ridge.
In the present invention, change the storage period t of drop on polymeric film surface, obtain the h～t variation relation of height h with drop t storage period of wetting ridge;
When described drop is when being greater than polymeric film time of relaxation the storage period on polymeric film surface, between the height of described drop storage period and described wetting ridge, there is the linear relationship shown in formula I;
Based on the slope k of formula I linear relationship, calculate the viscosity of polymeric film according to described formula II:
H=kt+b formula I,
Wherein, the height of the wetting ridge of h,
T drop in the storage period on polymeric film surface,
K slope,
B intercept;
η=0.37 γ sin θ/k formula II,
Wherein, the viscosity of η polymeric film,
The surface tension of γ drop,
The contact angle that θ drop and polymeric film surface are formed,
Slope in k formula I.
The present invention does not have special restriction for the method measuring the surface tension γ of drop described in formula II, adopts the technical scheme of the surface tension γ of mensuration drop well known to those skilled in the art. The present invention obtains the surface tension γ of drop or the surface tension γ that sheet method measures drop is hung in employing preferably by consulting document.
Adopt measuring method provided by the invention can measure substrate support polymer thin film viscosity accurately, and working method is simple, cost is low, wide adaptability.
Below in conjunction with the embodiment in the present invention, the technical scheme in the present invention is clearly and completely described. Obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments. Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
First, choosing the polymeric film that thickness is about 600nm, under this thickness, the viscosity of polymeric film is consistent with body. This patent scheme is utilized to measure the viscosity of this polymeric film, and the viscosity numerical value of the polymeric film adopting other method to obtain itself and document reported compares, to determine the feasibility of this scheme.
(1) utilize spin-coating film method, the toluene solution of polystyrene (PS, weight-average molecular weight is 1070kg/mol) is spin-coated on surface containing SiO2Silicon chip (the SiO of zone of oxidation2-Si) in substrate, prepare the PS film that thickness is 600nm; PS film is placed in the precise temperature control thermal station of 160 DEG C, and it is constant to maintain PS film temperature.
(2) 1-ethyl-3-methyl imidazolium tetrafluoroborate ([EIm] BF4) is positioned over PS film surface described in step (1), form drop, the surface tension γ of described drop=55mN/m, the DSA10-MK2 type contact angle tester utilizing Kruss company of Germany to produce measures the diameter of described drop for contact angle θ=78 ° of 2mm and described drop and the formation of described polymeric film surface.
(3) drop is after t storage period of polymeric film surface, utilize PS film described in the stainless steel plate cooling step (2) of 5 DEG C to room temperature, filter paper is utilized to exhaust the drop of described PS film surface, polymkeric substance/the drop of the PS film surface of described removing drop/air triple-phase line place forms wetting ridge, and Multimode-8 type atomic force microscope (AFM) utilizing U.S. Bruker to produce records the shape appearance figure (see Fig. 1) of described wetting ridge and the cross-sectional view (see Fig. 2) of wetting ridge shape looks;The height h of wetting ridge is obtained from the cross-sectional view of wetting ridge shape looks.
(4) change drop t storage period, obtain the cross-sectional view of a series of wetting ridge shape looks, see Fig. 3. Being mapped by drop t storage period with the height h of wetting ridge, as can be seen from Figure 4, after drop is greater than 10000 seconds storage period, the height of wetting ridge increases and linearly increase with drop storage period. The data that storage period is greater than 10000 seconds carry out linear fit, can obtain slope k=2.46 × 10 of h～t linear relationship- 11m/s。
Calculating at 160 DEG C according to formula II, weight-average molecular weight is the viscosity η=8.1 × 108Pa s of the PS film of 1070kg/mol.
By consulting document, document (Plazek, D.J.; O'Rourke, V.M.J.Polym.Sci, A:Polym.Phys.1971,9,209 243) to record, weight-average molecular weight is k value at 160 DEG C of the PS of 1070kg/mol is 1.84 × 109Pa s. Deviation between the two is less than an order of magnitude, in the scope of systematic error, it was demonstrated that the feasibility of measuring method of the present invention.
Embodiment 2
According to the method that embodiment 1 is identical, preparation weight-average molecular weight is the PS film of 442kg/mol, and the temperature maintaining described PS film is 170 DEG C. 1-own base-3-methyl imidazolium tetrafluoroborate ([HIm] BF4) is placed on PS film surface and forms drop, the surface tension of [HIm] BF4 drop is 35mN/m, and the contact angle that [HIm] BF4 drop and PS film surface are formed is 51 °. The relation of the change that the height of the wetting ridge of PS film surface occurs with drop increase storage period being measured, as can be seen from Figure 5, after the time is greater than 2000 seconds, wetting ridge height and drop are linear for storage period, its slope k=1.95 × 10- 10M/s. Calculating at 170 DEG C according to formula II, weight-average molecular weight is the viscosity η=5.2 × 107Pa s of the PS film of 442kg/mol.
By consulting document, document (Plazek, D.J.; O'Rourke, V.M.J.Polym.Sci, A:Polym.Phys.1971,9,209 243) to record, weight-average molecular weight is k value at 170 DEG C of the PS of 442kg/mol is 2.4 × 107Pa s. Deviation between the two is less than an order of magnitude, in the scope of systematic error, further demonstrate that the feasibility of measuring method of the present invention.
Embodiment 3
According to the method that embodiment 1 is identical, the temperature maintaining described PS film is 170 DEG C, 180 DEG C and 200 DEG C. Under measuring differing temps, the wetting ridge height of PS film surface, with the change of drop storage period, obtains the h～t relation line under differing temps, sees Fig. 6; And the slope k of h～t relation under obtaining differing temps. As can be seen from Figure 6,170 DEG C time k=5.9 × 10- 11M/s, k=9.7 × 10 when 180 DEG C- 11M/s, k=4.2 × 10 when 200 DEG C- 10M/s. Calculating at 170 DEG C, 180 DEG C and 200 DEG C according to formula II, the viscosity η that weight-average molecular weight is the PS film of 1070kg/mol is respectively 3.4 × 108Pa s, 2.0 × 108Pa s and 4.7 × 107Pa s.
As can be seen from Figure 7, measuring method of the present invention is utilized to be surveyed viscosity and document (Plazek, the D.J. of PS film under differing temps; O'Rourke, V.M.J.Polym.Sci, A:Polym.Phys.1971,9,209 243) record basically identical.
Embodiment 4
According to the method that embodiment 1 is identical, preparation weight-average molecular weight is the PS film of 168kg/mol, and the temperature maintaining described PS film is 130 DEG C, 140 DEG C, 145 DEG C and 150 DEG C.Under measuring differing temps, the wetting ridge height of PS film surface, with the change of drop storage period, obtains the h～t relation line under differing temps, sees Fig. 8; And the slope k of h～t relation under obtaining differing temps. As can be seen from Figure 8, temperature be 130 DEG C, 140 DEG C, 145 DEG C and when 150 DEG C corresponding slope k be respectively 4.6 × 10- 11m/s、1.3×10- 10m/s、6.8×10- 10M/s and 1.7 × 10- 9M/s. Calculating at 130 DEG C, 140 DEG C, 145 DEG C and 150 DEG C according to formula II, the viscosity η that weight-average molecular weight is the PS film of 168kg/mol is respectively 4.3 × 108Pa s, 1.5 × 108Pa s, 2.9 × 107Pa s and 1.2 × 107Pa s.
Embodiment 5
According to the method that embodiment 1 is identical, the PS film of preparation weight-average molecular weight to be 443kg/mol, thickness be 98nm. The change that the height of the wetting ridge of PS film surface occurs with drop increase storage period is measured, as seen from Figure 9, slope k=4.4 × 10, h～t linearity region- 10M/s. Calculating at 160 DEG C according to formula II, the viscosity η of the PS film of weight-average molecular weight to be 443kg/mol, thickness be 98nm is 4.5 × 107Pa s.
Embodiment 6
According to the method that embodiment 1 is identical, taking the silicon chip (H-Si) of surface passivation as substrate, the PS film of preparation weight-average molecular weight to be 443kg/mol, thickness be 68nm. The change that the height of the wetting ridge of PS film surface occurs with drop increase storage period is measured, as seen from Figure 10, slope k=1.4 × 10, h～t linearity region-10M/s. Calculating at 160 DEG C according to formula II, the viscosity η of the PS film of weight-average molecular weight to be 443kg/mol, thickness be 68nm is 1.4 × 108Pa s.
Embodiment 7
According to the method that embodiment 1 is identical, the PS film of preparation weight-average molecular weight to be 443kg/mol, thickness be 100～550nm, measures the viscosity η of PS film. As can be seen from Figure 11, after PS film thickness is less than 220nm, PS film viscosity reduces with film thickness and reduces.
For verifying the accuracy of result further, change base material, using the silicon chip (H-Si) of surface passivation as base material, measuring PS film thickness is within the scope of 69～700nm, and in H-Si substrate, the viscosity of PS film is with the variation relation of film thickness. As can be seen from Figure 11, along with the reduction of film thickness, the viscosity of PS film raises gradually. This with contain SiO with surface2The PS film viscosity that the silicon chip of zone of oxidation is substrate is contrary with the variation relation of thickness. This is caused by the difference interacted due to substrate and polymer interface. Owing to H-Si and PS has relatively strong interfacial interaction, the viscosity of PS film is caused to reduce with thickness and raise.
As can be seen from the above embodiments, measuring method provided by the invention can accurately measure the viscosity of substrate support polymeric film, the change of substrate support film viscosity had very strong susceptibility, it is possible to that experiences base property, polymeric film temperature and polymericular weight changes the impact on film viscosity simultaneously.
The above is only the preferred embodiment of the present invention; it is noted that for those skilled in the art, under the premise without departing from the principles of the invention; can also making some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a measuring method for substrate support polymer thin film viscosity, comprises the following steps:
(1) by the heating of substrate support polymeric film, also holding temperature is constant;
(2) test liquid is placed in the polymeric film surface that step (1) described holding temperature is constant, form drop, measure the contact angle θ value that described drop is formed on described polymeric film surface, the storage period t of record drop on polymeric film surface;
(3) polymeric film described in step (2) is cooled, remove the drop on described polymeric film surface, polymkeric substance/drop on the polymeric film surface of described removing drop/air triple-phase line place forms wetting ridge, measures the height h of wetting ridge;
(4) change the storage period t of drop on polymeric film surface, obtain the h～t variation relation of height h with drop t storage period of wetting ridge;
When described drop is when being greater than polymeric film time of relaxation the storage period on polymeric film surface, between the height of described drop storage period and described wetting ridge, there is the linear relationship shown in formula I;
Based on the slope k of formula I linear relationship, calculate the viscosity of polymeric film according to described formula II:
H=kt+b formula I,
Wherein, the height of the wetting ridge of h,
T drop in the storage period on polymeric film surface,
K slope,
B intercept;
η=0.37 γ sin θ/k formula II,
Wherein, the viscosity of η polymeric film,
The surface tension of γ drop,
The contact angle that θ drop and polymeric film surface are formed,
Slope in k formula I.
2. method according to claim 1, it is characterised in that, described in step (1), the thickness of polymeric film is 10～1000nm.
3. method according to claim 1, it is characterised in that, described in step (1), the thickness of polymeric film is 50～500nm.
4. method according to claim 1, it is characterised in that, in polymeric film described in step (1), polymkeric substance is linear polymer.
5. method according to claim 4, it is characterized in that, described linear polymer comprises the blend of one or more in polystyrene and derivative, methacrylate based polymers, polyvinyl tertbutyl ether, polyacrylonitrile, polymethacrylonitrile, polyvinyl acetate (PVA), polyphenylene oxide, polyvinyl chloride, polyvinylidene dichloride, vinyl fluoride base polymer, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, poly(lactic acid), nylon, polyhutadiene, polyisoprene, polysulfones, polyethers, or several multipolymers.
6. method according to claim 1, it is characterised in that, described in step (1), the temperature of heating is higher than the second-order transition temperature of polymkeric substance.
7. method according to claim 1, it is characterised in that, test liquid described in step (2) comprises glycerine, ethylene glycol, polyoxyethylene glycol oligopolymer, polyethylene oxide oligopolymer, dimethyl sulfoxide (DMSO), N, dinethylformamide or ionic liquid.
8. method according to claim 7, it is characterized in that, described ionic liquid comprises 1-ethyl-3-methyl imidazolium tetrafluoroborate, 1-own base-3-methyl imidazolium tetrafluoroborate, 1-butyl-3 Methylimidazole trifluoromethyl sulfonic acid or 1-butyl-3 Methylimidazole Methylsulfate.
9. method according to claim 1, it is characterised in that, described in step (2), the diameter of drop is 2～7mm.
10. method according to claim 1, it is characterised in that, cooling described in step (3) adopts heat-eliminating medium that described polymeric film is cooled to room temperature;
Described heat-eliminating medium comprises ice bag, liquid nitrogen, dry ice or low-temperature metal plate.
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