CN108728812B - Method for preparing film - Google Patents
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- CN108728812B CN108728812B CN201710269837.XA CN201710269837A CN108728812B CN 108728812 B CN108728812 B CN 108728812B CN 201710269837 A CN201710269837 A CN 201710269837A CN 108728812 B CN108728812 B CN 108728812B
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 208
- 239000010408 film Substances 0.000 claims abstract description 155
- 230000003287 optical effect Effects 0.000 claims abstract description 80
- 239000010409 thin film Substances 0.000 claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 70
- 229910052750 molybdenum Inorganic materials 0.000 claims description 70
- 239000011733 molybdenum Substances 0.000 claims description 70
- 238000004544 sputter deposition Methods 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 29
- 230000008033 biological extinction Effects 0.000 claims description 24
- 239000011521 glass Substances 0.000 claims description 22
- 238000002161 passivation Methods 0.000 claims description 19
- 230000010363 phase shift Effects 0.000 claims description 5
- 238000010586 diagram Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000000572 ellipsometry Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/542—Controlling the film thickness or evaporation rate
- C23C14/545—Controlling the film thickness or evaporation rate using measurement on deposited material
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/542—Controlling the film thickness or evaporation rate
- C23C14/545—Controlling the film thickness or evaporation rate using measurement on deposited material
- C23C14/547—Controlling the film thickness or evaporation rate using measurement on deposited material using optical methods
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The application discloses a method for determining the corresponding relation between optical parameters and preparation process parameters of a film, which is used for solving the problem that the properties such as density and the like of each layer of film cannot be quantitatively determined in the prior art and comprises the following steps: respectively preparing the thin films under a plurality of preset preparation technological parameters; and determining the optical parameters of each film prepared under the preset preparation process parameters to obtain the corresponding relation between the optical parameters of the film and the preparation process parameters so as to prepare the film meeting the preparation requirement according to the corresponding relation. A method of making a film is also disclosed.
Description
Technical Field
The present disclosure relates to the field of optoelectronic technologies, and in particular, to a method for manufacturing a thin film and a method for determining a correspondence between optical parameters of the thin film and manufacturing process parameters.
Background
With the development of micromachining processes, thin films are widely used in various fields, and among them, metal thin films are used in fields such as mechanics, electronics, magnetism, and optics. The film preparation process can be widely applied to the technical field of photoelectricity, such as copper indium gallium selenide (CuInGaSe)2CIGS) thin film solar cell.
In the process of preparing the thin film, the thin film with different densities is often prepared according to different requirements, for example, a molybdenum back electrode layer of the CIGS thin film solar cell often comprises a plurality of molybdenum films with different densities, wherein the first molybdenum film is used for being tightly combined with a substrate of the CIGS thin film solar cell, the performance of the solar cell is better when the porosity of the thin film is higher, and the performance of the solar cell is better when the density of the thin film is higher when the second molybdenum film is used for reducing the resistivity.
In the prior art, when films with different densities are expected to be prepared, the properties such as the densities of the films of each layer cannot be quantitatively determined.
Disclosure of Invention
The embodiment of the application provides a method for determining the corresponding relation between optical parameters and preparation process parameters of a film, which is used for solving the problem that the properties such as density and the like of each layer of film cannot be quantitatively determined in the prior art.
The embodiment of the application provides a method for preparing a film, which is used for solving the problem that the properties such as density and the like of each layer of film cannot be quantitatively determined in the prior art.
The embodiment of the application adopts the following technical scheme:
a method for determining the corresponding relation between optical parameters and preparation process parameters of a film comprises the following steps:
respectively preparing the thin films under a plurality of preset preparation technological parameters;
and determining the optical parameters of each film prepared under the preset preparation process parameters to obtain the corresponding relation between the optical parameters of the film and the preparation process parameters so as to prepare the film meeting the preparation requirement according to the corresponding relation.
A method of making a film comprising:
determining preparation process parameters and preparation time for preparing the film according to preparation requirements of the film to be prepared, a first corresponding relation and a second corresponding relation, wherein the preparation requirements comprise the thickness and the optical parameters of the film to be prepared, the first corresponding relation is the corresponding relation between the optical parameters of the film and the preparation process parameters, and the second corresponding relation is the corresponding relation between the preparation time and the thickness of the film;
and preparing the film according to the determined preparation process parameters and preparation time.
The embodiment of the application adopts at least one technical scheme which can achieve the following beneficial effects:
in the application, the preparation process parameters and the preparation time for preparing the film can be determined according to the preparation requirement of the film to be prepared, the first corresponding relation and the second corresponding relation, wherein the preparation requirement comprises the thickness and the optical parameters of the film to be prepared, the first corresponding relation is the corresponding relation between the optical parameters and the preparation process parameters of the film, the second corresponding relation is the corresponding relation between the preparation time and the thickness of the film, and then the film is prepared according to the determined preparation process parameters and the preparation time. In the application, the properties such as the density of the film are quantitatively characterized through the optical parameters of the film, so that the preparation requirement of the film can be quantitatively characterized through the optical parameters of the film, and when the film with certain density is expected to be prepared, the film meeting the preparation requirement can be prepared through the corresponding relation between the optical parameters and the preparation process parameters and by controlling the preparation process parameters.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
fig. 1 is a schematic structural diagram of a molybdenum back electrode layer according to an embodiment of the present disclosure;
FIG. 2 is a graph showing measured values and fitting values of a molybdenum film prepared at a sputtering gas pressure of 0.1Pa, which is provided in an example of the present application;
FIG. 3 is a graph showing measured values and fitting values of a molybdenum film prepared at a sputtering gas pressure of 0.2Pa according to an example of the present application;
FIG. 4 is a graph showing measured values and fitting values of a molybdenum film prepared at a sputtering gas pressure of 0.3Pa, provided in an example of the present application;
FIG. 5 is a graph showing measured values and fitting values of a molybdenum film prepared at a sputtering gas pressure of 0.7Pa, provided in examples of the present application;
FIG. 6 is a graph showing measured values and fitting values of a molybdenum film prepared at a sputtering gas pressure of 1Pa according to an example of the present application;
FIG. 7 is a graph showing the refractive index and extinction coefficient as a function of wavelength for molybdenum films prepared at a plurality of predetermined sputtering pressures provided by an example of the present application;
FIG. 8 is a graph showing the refractive index and extinction coefficient at 550nm as a function of sputtering gas pressure for molybdenum films prepared at a plurality of predetermined sputtering gas pressures provided in the examples herein;
fig. 9 is a schematic structural diagram of a molybdenum back electrode layer according to a first embodiment of the present disclosure;
fig. 10 is a schematic structural diagram of a molybdenum back electrode layer according to a second embodiment provided in an example of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the following specific embodiments of the present application and the accompanying drawings. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The technical solutions provided by the embodiments of the present application are described in detail below with reference to the accompanying drawings.
In order to solve the problem that the properties such as density and the like of each layer of thin film cannot be quantitatively determined in the prior art, the embodiment of the application provides a method for determining the corresponding relation between optical parameters of the thin film and preparation process parameters, and the implementation flow of the method comprises the following steps:
step 11, respectively preparing films under a plurality of preset preparation process parameters;
the preparation process parameters in the embodiment of the present application may be at least sputtering pressure, sputtering power, and other preparation process parameters. It should be noted that the thin film in the embodiment of the present application may be a metal thin film, such as molybdenum or titanium, or may be an inorganic thin film, such as a thin film of glass or silicon dioxide, which has a light-transmitting property.
Before films are respectively prepared under a plurality of preset preparation process parameters, a glass substrate for preparing the films can be cleaned, the surface of the cleaned glass substrate is dried, and then the films are prepared under the plurality of preset preparation process parameters by taking the glass substrate as a substrate. It will be clear to those skilled in the art that the plurality of predetermined manufacturing process parameters described herein are determined for a specific property of a certain film, and under these determined plurality of manufacturing process parameters, the optical parameters of the manufactured film and the corresponding manufacturing process parameters should have a certain corresponding relationship.
And step 12, determining optical parameters of each film prepared under a plurality of preset preparation process parameters to obtain a corresponding relation between the optical parameters of the film and the preparation process parameters, so as to prepare the film meeting the preparation requirement according to the corresponding relation.
Before determining the optical parameters of each film prepared under a plurality of preset preparation process parameters, first determining the first optical parameters of the glass substrate before the film is prepared after cleaning and drying, then respectively determining the second optical parameters of the glass substrate with each film, finally respectively determining the optical parameters of each film according to the first optical parameters and the second optical parameters of each film prepared, and establishing the corresponding relation between the preparation process parameters such as a plurality of preset sputtering air pressures, a plurality of preset sputtering powers and the like and the optical parameters of the first film, thereby obtaining the corresponding relation between the optical parameters of the films and the preparation process parameters. The optical parameters in the embodiments of the present application may include at least a refractive index, an extinction coefficient, and the like.
It should be noted that the first optical parameter and the second optical parameter in the embodiment of the present application are determined by the following method: firstly, an ellipsometer can be used for measuring an ellipsometry parameter of a measured medium, namely, the difference between the relative amplitude attenuation and the phase shift of the measured medium is determined; then, based on the determined difference between the relative amplitude attenuation and the phase shift, an optical parameter of the measured medium, which may be the glass substrate described above and/or a glass substrate prepared with a thin film, is determined. In addition, the optical parameter of the measured medium may be determined by first determining a reflection spectrum of the measured medium, then determining a difference between the relative amplitude attenuation and the relative displacement of the measured medium according to the reflection spectrum, and finally determining the difference between the relative amplitude attenuation and the relative displacement of the measured medium.
In the application, the films can be respectively prepared under a plurality of preset preparation process parameters, then the optical parameters of the films prepared under the plurality of preset preparation process parameters are determined, and the corresponding relation between the optical parameters of the films prepared under the plurality of preset preparation process parameters and the preparation process parameters is obtained, so that the films meeting the preparation requirements can be prepared according to the determined corresponding relation because the optical parameters of the films have direct corresponding relation with the properties such as density and the like, and the problem that the properties such as density and the like of each layer of film cannot be quantitatively determined in the prior art can be solved.
Based on the method for determining the corresponding relationship between the optical parameters of the film and the preparation process parameters, the embodiment of the application also provides a method for preparing the film, which is used for solving the problem that the properties such as the density and the like of each layer of film cannot be quantitatively determined in the prior art, and comprises the following steps:
step 21, determining preparation process parameters and preparation time for preparing the film according to the preparation requirement of the film to be prepared, the first corresponding relation and the second corresponding relation;
the preparation requirement comprises the thickness and the optical parameters of the film to be prepared, the first corresponding relation is the corresponding relation between the optical parameters of the film and the preparation process parameters, and the second corresponding relation is the corresponding relation between the preparation time and the thickness of the film. The preparation process parameters include at least one of sputtering gas pressure and sputtering power. The optical parameters include refractive index and extinction coefficient.
In order to facilitate quantitative determination of properties such as density of the thin film according to the preparation requirement of the thin film when the thin film is prepared, a corresponding relationship between an optical parameter of the thin film and a preparation process parameter, that is, a first corresponding relationship is predetermined in the embodiment of the present application, and a determination process of the first corresponding relationship is the above-mentioned corresponding relationship between the optical parameter of the thin film and the preparation process parameter, which will not be described herein again.
The second corresponding relation can be obtained by measuring the thickness and the preparation time of the film to be prepared by an ellipsometer, so as to obtain the deposition rate of the film, and further obtain the corresponding relation between the thickness and the preparation time of the film to be prepared, wherein the specific calculation formula of the deposition rate is as follows: deposition rate is thickness/time.
After the first corresponding relationship and the second corresponding relationship are determined, the preparation process parameters and the preparation time for preparing the film can be determined according to the preparation requirements of the film to be prepared, namely the optical parameters and the thickness of the film to be prepared, and the first corresponding relationship and the second corresponding relationship.
And step 22, preparing the film according to the determined preparation process parameters and preparation time.
After the preparation process parameters and the preparation time of the film to be prepared are determined, the film meeting the preparation requirements can be prepared according to the preparation process parameters and the preparation time.
In order to facilitate quantitative determination of the properties such as the density of each layer of the film of the molybdenum back electrode layer in combination with the same inventive concept as described above, and thereby to prepare a CIGS thin film solar cell with better performance, the method provided in the embodiments of the present application will be described in detail below by taking the preparation of the molybdenum back electrode layer as an example.
With the increasing exhaustion of energy and the increasing increase of environmental pollution, solar energy has gradually attracted extensive attention as an infinitely renewable pollution-free energy source of the earth, wherein a CIGS thin-film solar cell only needs a thickness of a few micrometers to realize photoelectric conversion, is an ideal material for reducing cost and improving photon cycle, and becomes a cell with the most potential in the future. A CIGS thin-film solar cell generally consists of a substrate, a back electrode, a CIGS absorber layer, a CdS buffer layer, a ZnO window layer, a transparent electrode, and an aluminum electrode. Since the molybdenum back electrode layer is directly in contact with the CIGS absorber layer, the performance of the CIGS absorber layer will be directly affected, thereby affecting the performance of the entire thin film solar cell.
The present embodiment provides a preferred implementation manner, and as shown in fig. 1, is a schematic structural diagram of a molybdenum back electrode layer provided in this embodiment, where the molybdenum back electrode layer includes a loose layer, a dense layer, and a passivation layer. Wherein the loose layer is used for being tightly combined with the substrate, the compact layer is used for reducing the resistivity, and the passivation layer is used for controlling the growth of the CIGS absorption layer. The preparation of the molybdenum back electrode layer can comprise the following steps:
step 31, determining a first preparation process parameter and a first preparation time of the loose layer, a second preparation process parameter and a second preparation time of the dense layer, and a third preparation process parameter and a third preparation time of the passivation layer according to the preparation requirement, the first corresponding relation and the second corresponding relation of the molybdenum back electrode layer to be prepared;
the preparation requirement comprises the thickness and optical parameters of the molybdenum back electrode layer to be prepared, the first corresponding relation is the corresponding relation between the optical parameters of the molybdenum film and the preparation process parameters, and the second corresponding relation is the corresponding relation between the preparation time and the thickness of the molybdenum film. The optical parameters include refractive index and extinction coefficient. The preparation process parameters comprise sputtering gas pressure and/or sputtering power.
In order to quantitatively determine the properties such as the density and the like of each molybdenum film of a molybdenum back electrode layer when the molybdenum back electrode layer is prepared, the embodiment of the application determines the corresponding relationship between the optical parameters of the molybdenum film and the preparation process parameters in advance, namely a first corresponding relationship, and comprises the following steps:
the method comprises the steps of firstly cleaning a glass substrate, then determining a first parameter Is and a second parameter Ic of the glass substrate, and finally determining optical parameters of the glass substrate, namely the refractive index and the extinction coefficient of the glass substrate according to the first parameter Is and the second parameter Ic, wherein the first parameter Is sin (2 psi) × sin (delta), the second parameter Ic sin (2 psi) × cos (delta), psi Is relative amplitude attenuation, delta Is a phase shift difference, and psi and delta can be measured by an ellipsometer.
And ii, preparing the molybdenum film by using the glass substrate as a substrate under a plurality of preset preparation process parameters. After determining the optical parameters of the glass substrate, the glass substrate is used as a substrate to prepare the molybdenum film under a plurality of preset preparation process parameters. The examples of the present application provide an alternative implementation of preparing a molybdenum film with a thickness in the range of 10 to 30nm using a glass substrate as a substrate under a plurality of predetermined sputtering pressures, i.e., sputtering pressures of 0.1Pa, 0.2Pa, 0.3Pa, 0.7Pa, and 1Pa, respectively.
And step iii, determining optical parameters of the molybdenum film prepared under a plurality of preset preparation process parameters to obtain a first corresponding relation. Ellipsometry parameters of the molybdenum films prepared at sputtering pressures of 0.1Pa, 0.2Pa, 0.3Pa, 0.7Pa and 1Pa in step ii are measured by an ellipsometer, and refractive indexes and extinction coefficients of the molybdenum films are determined according to the measured ellipsometry parameters, as shown in fig. 2 to 6, which are measured values and fitting values of the first parameter Is and the second parameter Ic of the molybdenum films prepared at sputtering pressures of 0.1Pa, 0.2Pa, 0.3Pa, 0.7Pa and 1Pa, respectively.
An optical model was established based on the fitted values of fig. 2 to 6, and the refractive index and extinction coefficient of the molybdenum film prepared under these five predetermined sputtering pressures were obtained as a function of wavelength, as shown in fig. 7. From fig. 7, the following conclusions can be drawn: when the sputtering gas pressure is lower, the refractive index and extinction coefficient of the molybdenum film are closer to those of the intrinsic metal molybdenum, and when the sputtering gas pressure is gradually increased from 0.1Pa to 1Pa, the refractive index and extinction coefficient of the molybdenum film are gradually reduced.
According to the Effective Medium Theory (EMT), the molybdenum film prepared under a plurality of predetermined preparation process parameters can be equivalent to a structure formed by mixing molybdenum and air, when the internal density of the molybdenum film is smaller, the refractive index and extinction coefficient of the molybdenum film are closer to those of air, and when the internal density of the molybdenum film is larger, the refractive index and extinction system of the molybdenum film are closer to those of intrinsic molybdenum. As shown in FIG. 8, the refractive index and extinction coefficient of the molybdenum film prepared under five predetermined sputtering pressures at a wavelength of 550nm are shown as a graph showing the change with the sputtering pressure. According to the graph 8, the sputtering gas pressure required by the preparation of the molybdenum film can be quantitatively calculated according to the compactness of the molybdenum film at the wavelength of 550 nm.
It should be noted that, in practical applications, since the loose layer is used to be tightly bonded to the substrate, a molybdenum film with lower density needs to be prepared as the loose layer, for example, a molybdenum film prepared under preparation process parameters corresponding to a refractive index n ∈ [2,3] and an extinction coefficient k ∈ [1,2.4] at a wavelength of 550nm, a molybdenum film with higher density needs to be prepared as the dense layer when the dense layer is used to reduce resistivity, for example, a molybdenum film prepared under preparation process parameters corresponding to a refractive index n ∈ [2,3] and an extinction coefficient k ∈ [1,2] at a wavelength of 550nm, and the passivation layer is used to control the growth of the CIGS absorption layer, and a molybdenum film with density between the loose layer and the dense layer needs to be prepared as the passivation layer.
The specific implementation manner of step 31 is to determine the optical parameters and thicknesses of the loose layer, the dense layer and the passivation layer respectively according to the preparation requirements of each layer of molybdenum film to be prepared, and then determine the preparation process parameters and preparation time for preparing the film according to the first corresponding relationship and the second corresponding relationship.
And step 32, respectively preparing the loose layer, the dense layer and the passivation layer according to the first preparation process parameter and the first preparation time, the second preparation process parameter and the second preparation time, and the third preparation process parameter and the third preparation time.
Firstly, preparing a first film on a glass substrate as a loose layer according to a first preparation process parameter and a first preparation time; then preparing a second film on the loose layer as a compact layer according to a second preparation process parameter and a second preparation time; and finally, preparing a third film on the dense layer as a passivation layer according to a third preparation process parameter and the third preparation time.
In the application, the preparation process parameters and the preparation time for preparing the film can be determined according to the preparation requirement of the film to be prepared, the first corresponding relation and the second corresponding relation, wherein the preparation requirement comprises the thickness and the optical parameters of the film to be prepared, the first corresponding relation is the corresponding relation between the optical parameters and the preparation process parameters of the film, the second corresponding relation is the corresponding relation between the preparation time and the thickness of the film, and then the film is prepared according to the determined preparation process parameters and the preparation time. In the application, the properties such as the density of the film are quantitatively characterized through the optical parameters of the film, so that the preparation requirement of the film can be quantitatively characterized through the optical parameters of the film, and when the film with certain density is expected to be prepared, the film meeting the preparation requirement can be prepared through the corresponding relation between the optical parameters and the preparation process parameters and by controlling the preparation process parameters. According to the present invention, the density/roughness of the prepared film is controlled by selecting an appropriate sputtering air pressure according to the corresponding relationship between the sputtering air pressure and optical parameters, and further, if necessary, the sputtering air pressure value can be adjusted by detecting whether a difference exists between the optical parameters of the prepared film and the expected optical parameters, so as to improve the quality of the finally prepared film.
The examples of the present application further provide two specific embodiments to explain in detail the implementation process of preparing the molybdenum back electrode layer:
as shown in fig. 9, a schematic structural diagram of a molybdenum back electrode layer according to a first specific embodiment is provided in an example of the present application, and a preparation process of the schematic structural diagram includes:
firstly, determining a first preparation process parameter (namely sputtering gas pressure of 1.0Pa) and a first preparation time of the loose layer according to preparation requirements of the loose layer, namely, the refractive index n of 2.85, the extinction coefficient k of 1.92 and the thickness of 150nm at the wavelength of 550nm, determining a second preparation process parameter (namely sputtering gas pressure of 0.2Pa) and a second preparation time of the dense layer according to preparation requirements of the dense layer, namely, the refractive index n of 3.63, the extinction coefficient k of 3.95 and the thickness of 800nm at the wavelength of 550nm, and determining a third preparation process parameter (namely sputtering gas pressure of 0.7Pa) and a third preparation time of the passivation layer according to preparation requirements of the passivation layer, namely, the refractive index n of 2.88, the extinction coefficient k of 2.82 and the thickness of 35nm at the wavelength of 550 nm;
and then respectively preparing the loose layer, the dense layer and the passivation layer according to the first preparation process parameter and the first preparation time, the second preparation process parameter and the second preparation time, and the third preparation process parameter and the third preparation time.
And (3) finishing the preparation of other layers of the CIGS thin-film solar cell on the molybdenum back electrode layer, and obtaining the Cu, In, Ga and Se percentage contents of the CIGS absorbing layer respectively 23.69%, 17.21%, 8.73% and 50.37% through X-ray fluorescence spectrum analysis. Voc, Jsc and FF of the CIGS thin-film solar cell without the prepared antireflection layer are respectively 0.5895V and 32.53A/cm2And 60.84, the efficiency of the CIGS thin film solar cell thus obtained was 11.67%.
As shown in fig. 10, a schematic structural diagram of a molybdenum back electrode layer according to a second specific embodiment is provided in an example of the present application, and a preparation process of the schematic structural diagram includes:
first, a first preparation process parameter (i.e., sputtering gas pressure of 1.0Pa) and a first preparation time of the bulk layer are determined according to preparation requirements of the bulk layer, i.e., a refractive index n of 2.85 at a wavelength of 550nm, an extinction coefficient k of 1.92, and a thickness of 150nm, preparation requirements of the dense layer, i.e., a refractive index n of 3.63 at a wavelength of 550nm, an extinction coefficient k of 4.00, and a preparation requirement of 800nm, a second preparation process parameter (i.e., sputtering gas pressure of 0.1Pa) and a second preparation time of the dense layer are determined, and preparation requirements of the passivation layer, i.e., a refractive index n of 2.88 at a wavelength of 550nm, an extinction coefficient k of 2.82, and a preparation requirement of 35nm, a third preparation process parameter (i.e., sputtering gas pressure of 0.7Pa) and a third preparation time of the passivation layer are determined.
And then respectively preparing the loose layer, the dense layer and the passivation layer according to the first preparation process parameter and the first preparation time, the second preparation process parameter and the second preparation time, and the third preparation process parameter and the third preparation time.
And (3) finishing the preparation of other layers of the CIGS thin-film solar cell on the molybdenum back electrode layer, and obtaining the CIGS absorbing layer with the percentage contents of Cu, In, Ga and Se of 24.50%, 16.61%, 9.29% and 49.60% respectively through X-ray fluorescence spectrum analysis. Voc, Jsc and FF of CIGS thin-film solar cells without prepared antireflection layers are 634.3m V and 32.21A/cm respectively2And 72.64, the efficiency of the CIGS thin film solar cell thus obtained was 14.84%.
When the extinction coefficient of the compact layer of the molybdenum back electrode layer is large, the compactness of the film is large, the efficiency of the CIGS film solar cell is often high, and then appropriate preparation process parameters can be selected according to the corresponding relation between the predetermined preparation process parameters and the optical parameters, so that the molybdenum back electrode layer meeting the preparation requirements can be accurately obtained, and the film solar cell with high photoelectric conversion efficiency can be obtained.
The method for preparing the thin film can quantitatively determine the properties such as the density of each layer of the thin film, and the like, and a person skilled in the art can understand that the quantitative determination is not completely accurate but within an allowable error range when the properties such as the density of the thin film are quantitatively determined through optical parameters due to the influence of various uncertain factors such as a measuring method, a measuring tool, a thin film preparation method, a preparation tool and the like.
It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in the process, method, article, or apparatus that comprises the element.
The above are merely examples of the present application and are not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (9)
1. A method for determining the corresponding relation between optical parameters and preparation process parameters of a film is characterized by comprising the following steps:
respectively preparing the thin films under a plurality of preset preparation technological parameters;
determining optical parameters of each film prepared under the preset preparation process parameters to obtain a corresponding relation between the optical parameters of the film and the preparation process parameters so as to prepare the film meeting the preparation requirement according to the corresponding relation; determining optical parameters of each thin film prepared under the plurality of preset preparation process parameters, specifically comprising:
determining a first optical parameter of the glass substrate;
determining a second optical parameter of the glass substrate on which the film is prepared;
determining an optical parameter of the film based on the first optical parameter and the second optical parameter.
2. The method of claim 1, wherein the first optical parameter and the second optical parameter are determined by:
determining the difference between the relative amplitude attenuation and the phase shift of a measured medium, wherein the measured medium comprises the glass substrate and/or the glass substrate provided with the thin film;
and determining the optical parameters of the measured medium according to the difference between the relative amplitude attenuation and the phase shift.
3. The method of claim 1, wherein the manufacturing process parameters include at least sputtering gas pressure and the optical parameters include at least refractive index and extinction coefficient.
4. A method of making a film, comprising:
determining preparation process parameters and preparation time for preparing the film according to preparation requirements of the film to be prepared, a first corresponding relation and a second corresponding relation, wherein the preparation requirements comprise the thickness and the optical parameters of the film to be prepared, the first corresponding relation is the corresponding relation between the optical parameters of the film and the preparation process parameters, and the second corresponding relation is the corresponding relation between the preparation time and the thickness of the film;
and preparing the film according to the determined preparation process parameters and preparation time.
5. The method of claim 4, wherein the manufacturing process parameters include at least sputtering gas pressure and the optical parameters include at least refractive index and extinction coefficient.
6. The method according to claim 4, wherein when the thin film is a molybdenum back electrode layer, the molybdenum back electrode layer comprises a loose layer, a dense layer and a passivation layer, and the preparation process parameters and the preparation time for preparing the thin film are determined according to the preparation requirement, the first corresponding relation and the second corresponding relation of the thin film to be prepared, and specifically comprise:
determining a first preparation process parameter and a first preparation time of the loose layer, a second preparation process parameter and a second preparation time of the dense layer, and a third preparation process parameter and a third preparation time of the passivation layer according to a preparation requirement, a first corresponding relation and a second corresponding relation of the molybdenum back electrode layer to be prepared, wherein the preparation requirement comprises the thickness and the optical parameter of the molybdenum back electrode layer to be prepared, the first corresponding relation is a corresponding relation of the optical parameter and the preparation process parameter of the molybdenum film, and the second corresponding relation is a corresponding relation of the preparation time and the thickness of the molybdenum film.
7. The method according to claim 6, wherein when the thin film is a molybdenum back electrode layer, the preparing the thin film according to the determined preparation process parameters and preparation time specifically comprises:
and respectively preparing the loose layer, the dense layer and the passivation layer according to the first preparation process parameter and the first preparation time, the second preparation process parameter and the second preparation time, and the third preparation process parameter and the third preparation time.
8. The method according to claim 7, wherein the preparing the bulk layer, the dense layer and the passivation layer according to the first preparation process parameter and the first preparation time, the second preparation process parameter and the second preparation time, and the third preparation process parameter and the third preparation time, respectively, comprises:
preparing a first film on the glass substrate as the loose layer according to the first preparation process parameter and the first preparation time;
preparing a second film on the loose layer as the compact layer according to the second preparation process parameter and the second preparation time;
and preparing a third film on the dense layer as the passivation layer according to the third preparation process parameter and the third preparation time.
9. The method according to any one of claims 4 to 8, wherein the first correspondence is determined by a method for determining correspondence between optical parameters and production process parameters of the thin film according to any one of claims 1 to 3.
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| CN101871093A (en) * | 2010-06-19 | 2010-10-27 | 大连交通大学 | Method for preparing selective absorbing coating for steel core of solar collection tube |
| CN106017338A (en) * | 2016-05-26 | 2016-10-12 | 国家纳米科学中心 | Method for determining film continuity critical thickness |
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| CN101871093A (en) * | 2010-06-19 | 2010-10-27 | 大连交通大学 | Method for preparing selective absorbing coating for steel core of solar collection tube |
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