CN112885718B - Preparation method of composite conductive film - Google Patents
Preparation method of composite conductive film Download PDFInfo
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- CN112885718B CN112885718B CN202110075647.0A CN202110075647A CN112885718B CN 112885718 B CN112885718 B CN 112885718B CN 202110075647 A CN202110075647 A CN 202110075647A CN 112885718 B CN112885718 B CN 112885718B
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- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 25
- 239000010410 layer Substances 0.000 claims abstract description 144
- 239000002346 layers by function Substances 0.000 claims abstract description 89
- 238000005137 deposition process Methods 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 79
- 230000008021 deposition Effects 0.000 claims description 77
- 239000007789 gas Substances 0.000 claims description 65
- 229910052786 argon Inorganic materials 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 150000002500 ions Chemical class 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 20
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims description 9
- 230000036470 plasma concentration Effects 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 12
- 230000035515 penetration Effects 0.000 abstract description 8
- 238000007738 vacuum evaporation Methods 0.000 abstract description 7
- 238000000151 deposition Methods 0.000 description 53
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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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
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
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Abstract
The application discloses a method for preparing a composite conductive film, which adopts a reactive plasma deposition process to prepare a first ohmic contact layer, a first functional layer, a current conduction layer, a second functional layer and a second ohmic contact layer, avoids the problem of larger accumulated stress of films prepared by the traditional processes of vacuum evaporation, magnetron sputtering and the like, and avoids the condition of damaging a substrate, meanwhile, when the first functional layer is prepared, the flow of introduced first preset gas is increased along with time to reduce the growth stress of the film layer and realize the purpose of preparing a low-stress film, and when the second functional layer is prepared, the flow of introduced second preset gas is reduced along with the increase of time to reduce the growth stress of the film layer and realize the purpose of preparing the low-stress film, and the specific stack structure of the first ohmic contact layer, the first functional layer, the current conduction layer, the second functional layer and the second ohmic contact layer is combined, the purpose of preparing the transparent conductive film with low resistance, high penetration rate and high stability is achieved.
Description
Technical Field
The application relates to the technical field of semiconductors, in particular to a preparation method of a composite conductive film.
Background
The transparent conductive film is widely applied to the technical fields of light emitting diodes, solar cells, flat panel display and the like.
How to prepare transparent conductive films with low resistance, high transmittance and high stability is one of the directions of efforts of researchers.
Disclosure of Invention
In order to solve the technical problems, the application provides a preparation method of a composite conductive film, so as to achieve the purpose of preparing a transparent conductive film with low resistance, high penetration rate and high stability.
In order to achieve the technical purpose, the embodiment of the application provides the following technical scheme:
a preparation method of a composite conductive film comprises the following steps:
providing a substrate;
preparing a first ohmic contact layer, a first functional layer, a current conducting layer, a second functional layer and a second ohmic contact layer on the surface of the substrate in sequence by adopting a reactive plasma deposition process;
when the first functional layer is prepared by adopting a reactive plasma deposition process, the flow of the introduced first preset gas is increased along with the increase of time;
when the second functional layer is prepared by adopting a reactive plasma deposition process, the flow of the introduced second preset gas is reduced along with the increase of time.
Optionally, the step of sequentially preparing the first ohmic contact layer, the first functional layer, the current conducting layer, the second functional layer and the second ohmic contact layer on the surface of the substrate by using a reactive plasma deposition process includes:
preparing the first ohmic contact layer by adopting a reactive plasma deposition process, wherein the plasma concentration is controlled to be lower than a first preset concentration in the preparation process, and the current of the magnetic coil is controlled to be larger than a first preset current;
preparing the first functional layer by adopting a reactive plasma deposition process, wherein the flow of introduced oxygen and argon are controlled to increase along with the increase of time in the preparation process;
preparing the current conducting layer by adopting a reactive plasma deposition process, wherein the concentration of introduced oxygen is controlled to be greater than a second preset concentration in the preparation process, and the concentration of ions is controlled to be greater than a third preset concentration;
preparing the second functional layer by adopting a reactive plasma deposition process, wherein the flow of the introduced second preset gas is controlled to be reduced along with the increase of time in the preparation process;
and preparing the second ohmic contact layer by adopting a reactive plasma deposition process, wherein the flow of the introduced oxygen is controlled to be smaller than a fourth preset concentration, and the flow of the introduced argon is controlled to be smaller than a fifth preset concentration.
Optionally, the preparing the first ohmic contact layer by using a reactive plasma deposition process includes:
preparing a first ohmic contact layer with the thickness of 20-100 angstroms under a first preset condition;
the first preset condition includes: argon gas with the flow rate of 70-80 sccm is introduced through a reaction ion gun of the reaction plasma deposition equipment, the value of the current of a magnetic coil of the reaction plasma deposition equipment is controlled within the range of 50-75A, target process gas is introduced into a cavity of the reaction plasma deposition equipment, the target process gas comprises oxygen with the flow rate of 0-5 sccm and argon gas with the flow rate of 40-60 sccm, and the value range of background vacuum of the reaction plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
Optionally, the preparing the first functional layer by using a reactive plasma deposition process includes:
preparing a first functional layer with the thickness of 50-100 angstroms under a second preset condition;
the second preset condition includes: introducing argon gas through a reactive ion gun of the reactive plasma deposition equipment, wherein the flow rate of the introduced argon gas is increased from 50sccm to 110sccm in a step length of 10sccm, introducing oxygen gas into a cavity of the reactive plasma deposition equipment, the flow rate of the introduced oxygen gas is increased from 10sccm to 40sccm in a step length of 5sccm, and the value range of the background vacuum of the reactive plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
Optionally, the preparing the current conducting layer by using a reactive plasma deposition process includes:
under a third preset condition, preparing a current conducting layer with the thickness of 200-1000 angstroms;
the third preset condition includes: argon gas with the flow of 40-50 sccm is introduced through a reaction ion gun of the reaction plasma deposition equipment, the value of the current of a magnetic coil of the reaction plasma deposition equipment is controlled within the range of 20-25A, target process gas is introduced into a cavity of the reaction plasma deposition equipment,the target material process gas comprises oxygen with the flow rate of 45-50 sccm and argon with the flow rate of 100-120 sccm, and the value range of the background vacuum of the reactive plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
Optionally, the preparing the second functional layer by using a reactive plasma deposition process includes:
preparing a second functional layer with the thickness of 50-100 angstroms under a fourth preset condition;
the fourth preset condition includes: introducing argon gas through a reactive ion gun of the reactive plasma deposition equipment, wherein the flow rate of the introduced argon gas is gradually reduced from 110sccm to 50sccm by taking 10sccm as a step length, introducing oxygen gas into a cavity of the reactive plasma deposition equipment, the flow rate of the introduced oxygen gas is gradually reduced from 40sccm to 5sccm by taking 5sccm as a step length, and the value range of the background vacuum of the reactive plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
Optionally, the preparing the second ohmic contact layer by using a reactive plasma deposition process includes:
preparing a second ohmic contact layer with the thickness of 20-100 angstroms under a fifth preset condition;
the fifth preset condition includes: argon gas with the flow rate of 70-80 sccm is introduced through a reaction ion gun of the reaction plasma deposition equipment, the value of the current of a magnetic coil of the reaction plasma deposition equipment is controlled within the range of 50-75A, target process gas is introduced into a cavity of the reaction plasma deposition equipment, the target process gas comprises oxygen with the flow rate of 0-5 sccm and argon gas with the flow rate of 40-60 sccm, and the value range of background vacuum of the reaction plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
Optionally, after the preparing the first functional layer by using the reactive plasma deposition process, before the preparing the current conducting layer by using the reactive plasma deposition process, the method further includes:
and carrying out primary annealing treatment on the substrate and the surface film layer thereof, wherein the temperature range of the primary annealing treatment is 250-350 ℃, and the annealing time range is 5-15 min.
Optionally, after the preparing the current conducting layer by using the reactive plasma deposition process, before the preparing the second functional layer by using the reactive plasma deposition process, the method further includes:
and carrying out secondary annealing treatment on the substrate and the surface film layer thereof, wherein the temperature range of the secondary annealing treatment is 250-350 ℃, and the annealing time range is 5-15 min.
Optionally, after the providing of the substrate, before the preparing of the first ohmic contact layer, the first functional layer, the current conducting layer, the second functional layer, and the second ohmic contact layer on the surface of the substrate in sequence by using the reactive plasma deposition process, the method further includes:
placing the substrate into a cavity of a reactive plasma deposition device for preheating treatment, wherein the temperature of the cavity ranges from 100 to 200 ℃ during preheating treatment, the preheating time ranges from 15 to 50min, and the background vacuum ranges from 2.0 x 10-4～3.0×10-4Pa。
It can be seen from the above technical solutions that the embodiments of the present application provide a method for preparing a composite conductive film, in which a reactive plasma deposition process is used to prepare a first ohmic contact layer, a first functional layer, a current conduction layer, a second functional layer, and a second ohmic contact layer, so as to avoid the problem of a large accumulated stress of a film prepared by conventional processes such as vacuum evaporation and magnetron sputtering, and also avoid the situation that a substrate may be damaged by the processes such as magnetron sputtering, and at the same time, when preparing the first functional layer, the flow rate of a first preset gas introduced is increased with time to reduce the growth stress of the film, thereby achieving the purpose of preparing a low-stress film, and when preparing the second functional layer, the flow rate of a second preset gas introduced is decreased with time to reduce the growth stress of the film, thereby achieving the purpose of preparing a low-stress film, the transparent conductive film with low resistance, high penetration rate and high stability is prepared by combining a specific first ohmic contact layer, a first functional layer, a current conduction layer, a second functional layer and a second ohmic contact layer stacking structure.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, it is obvious that the drawings in the following description are only embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for manufacturing a composite conductive film according to an embodiment of the present disclosure;
FIG. 2 is a schematic structural diagram of a composite conductive film according to an embodiment of the present disclosure;
fig. 3 is a schematic flow chart of a method for manufacturing a composite conductive film according to another embodiment of the present application;
FIG. 4 is a schematic flow chart illustrating a method for fabricating a composite conductive film according to yet another embodiment of the present disclosure;
fig. 5 is a schematic flow chart of a method for manufacturing a composite conductive film according to still another embodiment of the present application.
Detailed Description
As described in the background art, the method for preparing the transparent conductive film in the prior art mainly comprises vacuum evaporation, magnetron sputtering, electron beam evaporation and the like, wherein the atomic energy generated by the vacuum evaporation and the electron beam evaporation is low, the compactness of the film layer is poor, and the compactness of the transparent conductive film prepared by the magnetron sputtering is good, but high-energy ions exceeding 100ev exist in the magnetron sputtering preparation process, high-energy ion bombardment damage is generated on a substrate, and the performance requirements of low resistance, high penetration rate and the like are difficult to realize by a single transparent conductive film. In addition, the growth stress of the film layer is gradually accumulated to be larger in the preparation process of the single film.
In order to solve the problem, an embodiment of the present application provides a method for preparing a composite conductive film, including:
providing a substrate;
preparing a first ohmic contact layer, a first functional layer, a current conducting layer, a second functional layer and a second ohmic contact layer on the surface of the substrate in sequence by adopting a reactive plasma deposition process;
when the first functional layer is prepared by adopting a reactive plasma deposition process, the flow of the introduced first preset gas is increased along with the increase of time;
when the second functional layer is prepared by adopting a reactive plasma deposition process, the flow of the introduced second preset gas is reduced along with the increase of time.
The method adopts a reactive plasma deposition process to prepare a first ohmic contact layer, a first functional layer, a current conducting layer, a second functional layer and a second ohmic contact layer, avoids the problem of larger accumulated stress of films prepared by the traditional processes such as vacuum evaporation, magnetron sputtering and the like, also avoids the condition that the substrates are possibly damaged by the magnetron sputtering and the like, simultaneously, when the first functional layer is prepared, the flow of introduced first preset gas is increased along with the increase of time so as to reduce the growth stress of the films and realize the purpose of preparing the low-stress films, and similarly, when the second functional layer is prepared, the flow of introduced second preset gas is reduced along with the increase of time so as to reduce the growth stress of the films and realize the purpose of preparing the low-stress films, and the specific stack structure of the first ohmic contact layer, the first functional layer, the current conducting layer, the second functional layer and the second ohmic contact layer is combined, the purpose of preparing the transparent conductive film with low resistance, high penetration rate and high stability is achieved.
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part 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 embodiment of the application provides a preparation method of a composite conductive film, as shown in fig. 1, comprising the following steps:
s101: providing a substrate;
s102: preparing a first ohmic contact layer, a first functional layer, a current conducting layer, a second functional layer and a second ohmic contact layer on the surface of the substrate in sequence by adopting a reactive plasma deposition process;
when the first functional layer is prepared by adopting a reactive plasma deposition process, the flow of the introduced first preset gas is increased along with the increase of time;
when the second functional layer is prepared by adopting a reactive plasma deposition process, the flow of the introduced second preset gas is reduced along with the increase of time.
The structure of the obtained composite transparent conductive film is prepared with reference to fig. 2. And a second ohmic contact layer is deposited on the second functional layer, so that the contact resistance between the composite conductive film and the metal can be reduced. In fig. 2, reference numerals 10, 20, 30, 40, 50, and 60 denote the substrate, the first ohmic contact layer, the first functional layer, the current conducting layer, the second functional layer, and the second ohmic contact layer, respectively.
The preparation method of the composite conductive film provided by the embodiment of the application adopts a reactive plasma deposition process to prepare the first ohmic contact layer, the first functional layer, the current conduction layer, the second functional layer and the second ohmic contact layer, so that the problem of large accumulated stress of films prepared by the traditional processes such as vacuum evaporation, magnetron sputtering and the like is avoided, the situation that the substrate is possibly damaged by the magnetron sputtering and the like is also avoided, meanwhile, when the first functional layer is prepared, the flow of introduced first preset gas is increased along with the increase of time to reduce the growth stress of the film layer and realize the purpose of preparing the low-stress film, and when the second functional layer is prepared, the flow of introduced second preset gas is reduced along with the increase of time to reduce the growth stress of the film layer and realize the purpose of preparing the low-stress film, and the specific first ohmic contact layer and the specific first functional layer are combined, The current conducting layer, the second functional layer and the second ohmic contact layer are stacked, and the purpose of preparing the transparent conductive film with low resistance, high penetration rate and high stability is achieved.
Optionally, referring to fig. 3, after providing the substrate, before sequentially preparing the first ohmic contact layer, the first functional layer, the current conducting layer, the second functional layer, and the second ohmic contact layer on the surface of the substrate by using a reactive plasma deposition process, the method further includes:
s1012: placing the substrate into a cavity of a reactive plasma deposition device for preheating treatment, wherein the temperature of the cavity ranges from 100 to 200 ℃ during preheating treatment, the preheating time ranges from 15 to 50min, and the background vacuum ranges from 2.0 x 10-4～3.0×10-4Pa。
In the embodiment of the present application, the purpose of the additional step S1012 is to clean the substrate surface, so as to provide a good basis for the subsequent film growth.
A practical implementation manner of each step of the method for preparing a composite conductive film provided in the embodiment of the present application is described in detail below.
Referring to fig. 4, the sequentially preparing a first ohmic contact layer, a first functional layer, a current conducting layer, a second functional layer, and a second ohmic contact layer on the surface of the substrate by using a reactive plasma deposition process includes:
s1021: preparing the first ohmic contact layer by adopting a reactive plasma deposition process, wherein the plasma concentration is controlled to be lower than a first preset concentration in the preparation process, and the current of the magnetic coil is controlled to be larger than a first preset current;
in step S1021, the values of the first preset concentration and the first preset current are taken to ensure that the preparation environment of the first ohmic contact layer is the low plasma concentration assisted film deposition preparation and the high-heat electron bombardment evaporation equipment, and the method has the characteristic of no high-energy ion evaporation, and the whole process adopts low-temperature and low-oxygen conditions to form a low-resistance film.
S1022: preparing the first functional layer by adopting a reactive plasma deposition process, wherein the flow of introduced oxygen and argon are controlled to increase along with the increase of time in the preparation process;
s1023: preparing the current conducting layer by adopting a reactive plasma deposition process, wherein the concentration of introduced oxygen is controlled to be greater than a second preset concentration in the preparation process, and the concentration of ions is controlled to be greater than a third preset concentration;
in step S1023, the values of the second predetermined concentration and the third predetermined concentration are set to ensure that the current conducting layer is prepared in an environment with high oxygen concentration and high plasma concentration.
S1024: preparing the second functional layer by adopting a reactive plasma deposition process, wherein the flow of the introduced second preset gas is controlled to be reduced along with the increase of time in the preparation process;
s1025: and preparing the second ohmic contact layer by adopting a reactive plasma deposition process, wherein the flow of the introduced oxygen is controlled to be smaller than a fourth preset concentration, and the flow of the introduced argon is controlled to be smaller than a fifth preset concentration.
In step S1025, the fourth preset concentration and the fifth lossy concentration are set for the purpose of ensuring that the second ohmic contact layer is prepared under the conditions of low oxygen concentration and low argon concentration.
More specifically, referring to fig. 5, the preparing the first ohmic contact layer using the reactive plasma deposition process includes:
s10211: preparing a first ohmic contact layer with the thickness of 20-100 angstroms under a first preset condition;
the first preset condition includes: introducing argon gas with the flow of 70-80 sccm through a reaction ion gun of the reaction plasma deposition equipment, controlling the value of the current of a magnetic coil of the reaction plasma deposition equipment to be within the range of 50-75A, introducing target process gas into a cavity of the reaction plasma deposition equipment, wherein the target process gas comprises oxygen with the flow of 0-5 sccm and argon with the flow of 40-60 sccm, and the value of the background vacuum of the reaction plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃. Specifically, the value of the background vacuum of the reactive plasma deposition apparatus in the first preset condition may be selected to be 6.0 × 10-4Pa。
The preparing the first functional layer by using a reactive plasma deposition process comprises:
s10212: preparing a first functional layer with the thickness of 50-100 angstroms under a second preset condition;
the second preset condition includes: introducing argon gas through a reaction ion gun of the reaction plasma deposition equipment, wherein the flow rate of the introduced argon gas is increased to 110sccm from 50sccm by taking 10sccm as a step length, introducing oxygen gas into a cavity of the reaction plasma deposition equipment, the flow rate of the introduced oxygen gas is increased to 40sccm by taking 5sccm as the step length from 10sccm, and the value range of the background vacuum of the reaction plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃. Specifically, the value of the background vacuum of the reactive plasma deposition apparatus in the second preset condition may be selected to be 6.0 × 10-4Pa。
The preparing the current conducting layer by using a reactive plasma deposition process comprises:
s10213: under a third preset condition, preparing a current conducting layer with the thickness of 200-1000 angstroms;
the third preset condition includes: introducing argon gas with the flow rate of 40-50 sccm through a reaction ion gun of the reaction plasma deposition equipment, controlling the value of the current of a magnetic coil of the reaction plasma deposition equipment to be within the range of 20-25A, introducing target process gas into a cavity of the reaction plasma deposition equipment, wherein the target process gas comprises oxygen with the flow rate of 45-50 sccm and argon gas with the flow rate of 100-120 sccm, and the value range of background vacuum of the reaction plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
The preparation of the second functional layer by using the reactive plasma deposition process comprises the following steps:
s10214: preparing a second functional layer with the thickness of 50-100 angstroms under a fourth preset condition;
the fourth preset condition includes: introducing argon gas through a reactive ion gun of the reactive plasma deposition equipment, wherein the flow rate of the introduced argon gas is reduced to 50sccm from 110sccm by taking 10sccm as a step length, introducing oxygen into the cavity of the reactive plasma deposition equipment, and the flow rate of the introduced oxygen gas is reduced from 40sccm to 5sccmThe sccm is the step length and is reduced to 5sccm, and the value range of the background vacuum of the reactive plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃. Specifically, the value of the background vacuum of the reactive plasma deposition apparatus in the fourth preset condition may be selected to be 6.0 × 10-4Pa。
The preparing the second ohmic contact layer by using the reactive plasma deposition process includes:
s10215: preparing a second ohmic contact layer with the thickness of 20-100 angstroms under a fifth preset condition;
the fifth preset condition includes: argon gas with the flow rate of 70-80 sccm is introduced through a reaction ion gun of the reaction plasma deposition equipment, the value of the current of a magnetic coil of the reaction plasma deposition equipment is controlled within the range of 50-75A, target process gas is introduced into a cavity of the reaction plasma deposition equipment, the target process gas comprises oxygen with the flow rate of 0-5 sccm and argon gas with the flow rate of 40-60 sccm, and the value range of background vacuum of the reaction plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃. Specifically, the value of the background vacuum of the reactive plasma deposition apparatus in the fifth preset condition may be selected to be 6.0 × 10-4Pa。
In step S10212, the argon and oxygen are gradually increased in a step shape during the first functional layer coating to reduce the film growth stress and form a low stress film.
In step S10215, the second ohmic contact layer is a low-stress film formed by plating under low-oxygen and low-argon conditions.
In step S10213, the current conducting layer is prepared with high oxygen and high ion concentration to achieve high penetration.
In step S10214, a second functional layer is formed on the current conducting layer, and argon and oxygen are gradually reduced in a step shape during plating.
Optionally, referring to fig. 5, in a specific embodiment of the present application, after the preparing the first functional layer by using the reactive plasma deposition process, before the preparing the current conducting layer by using the reactive plasma deposition process, the method further includes:
s103: and carrying out primary annealing treatment on the substrate and the surface film layer thereof, wherein the temperature range of the primary annealing treatment is 250-350 ℃, and the annealing time range is 5-15 min.
After the current conducting layer is prepared by adopting the reactive plasma deposition process, before the second functional layer is prepared by adopting the reactive plasma deposition process, the method further comprises the following steps:
s104: and carrying out secondary annealing treatment on the substrate and the surface film layer thereof, wherein the temperature range of the secondary annealing treatment is 250-350 ℃, and the annealing time range is 5-15 min.
In this embodiment, the stress relief treatment is performed by performing a medium-temperature thermal annealing in the chamber between the processes of the first functional layer and the current conducting layer, and the stress relief treatment is performed by performing a medium-temperature thermal annealing in the chamber between the processes of the current conducting layer and the second functional layer.
To sum up, the embodiment of the present application provides a method for preparing a composite conductive film, which employs a reactive plasma deposition process to prepare a first ohmic contact layer, a first functional layer, a current conduction layer, a second functional layer and a second ohmic contact layer, thereby avoiding the problem of large accumulated stress of films prepared by conventional processes such as vacuum evaporation and magnetron sputtering, and also avoiding the damage to a substrate by the magnetron sputtering, and meanwhile, when preparing the first functional layer, the flow rate of the introduced first preset gas is increased with the increase of time to reduce the film growth stress and realize the purpose of preparing a low-stress film, and when preparing the second functional layer, the flow rate of the introduced second preset gas is reduced with the increase of time to reduce the film growth stress and realize the purpose of preparing the low-stress film, and the method combines a specific first ohmic contact layer, a specific second ohmic contact layer, and a specific first ohmic contact layer are formed on the substrate, and the substrate are formed by a specific first ohmic contact layer, and a second ohmic contact layer, and a specific first ohmic contact layer, and a second ohmic contact layer are formed on the first ohmic contact layer, and a second ohmic contact layer, wherein the first ohmic contact layer are formed on the first ohmic contact layer, and a second ohmic contact layer, and a second layer, which are formed on the second layer, and a second layer, which are formed on the second layer, and a second layer, are formed on the second layer, which are formed on the first layer, and a second layer, which are formed on the second layer, and a second layer, are formed on the second layer, which is formed on the second layer, are formed on the second layer, and a second layer, which are formed on the substrate, and a second layer, which are formed on the second layer, and a second, The first functional layer, the current conducting layer, the second functional layer and the second ohmic contact layer are stacked to achieve the purpose of preparing the transparent conductive film with low resistance, high penetration rate and high stability.
Features described in the embodiments in the present specification may be replaced with or combined with each other, each embodiment is described with a focus on differences from other embodiments, and the same and similar portions among the embodiments may be referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a composite conductive film is characterized by comprising the following steps:
providing a substrate;
preparing a first ohmic contact layer, a first functional layer, a current conducting layer, a second functional layer and a second ohmic contact layer on the surface of the substrate in sequence by adopting a reactive plasma deposition process;
when the first functional layer is prepared by adopting a reactive plasma deposition process, the flow of the introduced first preset gas is increased along with the increase of time;
when the second functional layer is prepared by adopting a reactive plasma deposition process, the flow of the introduced second preset gas is reduced along with the increase of time.
2. The method of claim 1, wherein the sequentially preparing a first ohmic contact layer, a first functional layer, a current conducting layer, a second functional layer and a second ohmic contact layer on the surface of the substrate by using a reactive plasma deposition process comprises:
preparing the first ohmic contact layer by adopting a reactive plasma deposition process, wherein the plasma concentration is controlled to be lower than a first preset concentration in the preparation process, and the current of the magnetic coil is controlled to be larger than a first preset current;
preparing the first functional layer by adopting a reactive plasma deposition process, wherein the flow of introduced oxygen and argon are controlled to increase along with the increase of time in the preparation process;
preparing the current conducting layer by adopting a reactive plasma deposition process, wherein the concentration of introduced oxygen is controlled to be greater than a second preset concentration in the preparation process, and the concentration of ions is controlled to be greater than a third preset concentration;
preparing the second functional layer by adopting a reactive plasma deposition process, wherein the flow of the introduced second preset gas is controlled to be reduced along with the increase of time in the preparation process;
and preparing the second ohmic contact layer by adopting a reactive plasma deposition process, wherein the flow of the introduced oxygen is controlled to be smaller than a fourth preset concentration, and the flow of the introduced argon is controlled to be smaller than a fifth preset concentration.
3. The method of claim 2, wherein the fabricating the first ohmic contact layer using a reactive plasma deposition process comprises:
preparing a first ohmic contact layer with the thickness of 20-100 angstroms under a first preset condition;
the first preset condition includes: argon gas with the flow rate of 70-80 sccm is introduced through a reaction ion gun of the reaction plasma deposition equipment, the value of the current of a magnetic coil of the reaction plasma deposition equipment is controlled within the range of 50-75A, target process gas is introduced into a cavity of the reaction plasma deposition equipment, the target process gas comprises oxygen with the flow rate of 0-5 sccm and argon gas with the flow rate of 40-60 sccm, and the value range of background vacuum of the reaction plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
4. The method of claim 2, wherein said preparing said first functional layer using a reactive plasma deposition process comprises:
preparing a first functional layer with the thickness of 50-100 angstroms under a second preset condition;
the second preset condition includes: introducing argon gas through a reactive ion gun of the reactive plasma deposition equipment, wherein the flow rate of the introduced argon gas is increased from 50sccm to 110sccm in a step length of 10sccm, introducing oxygen gas into a cavity of the reactive plasma deposition equipment, the flow rate of the introduced oxygen gas is increased from 10sccm to 40sccm in a step length of 5sccm, and the value range of the background vacuum of the reactive plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
5. The method of claim 2, wherein said fabricating said current conducting layer using a reactive plasma deposition process comprises:
under a third preset condition, preparing a current conducting layer with the thickness of 200-1000 angstroms;
the third preset condition comprises: introducing argon gas with the flow rate of 40-50 sccm through a reaction ion gun of the reaction plasma deposition equipment, controlling the value of the current of a magnetic coil of the reaction plasma deposition equipment to be within the range of 20-25A, introducing target process gas into a cavity of the reaction plasma deposition equipment, wherein the target process gas comprises oxygen with the flow rate of 45-50 sccm and argon gas with the flow rate of 100-120 sccm, and the value range of background vacuum of the reaction plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
6. The method of claim 2, wherein said preparing said second functional layer using a reactive plasma deposition process comprises:
preparing a second functional layer with the thickness of 50-100 angstroms under a fourth preset condition;
the fourth preset condition includes: introducing argon gas through a reactive ion gun of the reactive plasma deposition equipment, wherein the flow rate of the introduced argon gas is reduced to 50sccm from 110sccm by taking 10sccm as a step length, introducing oxygen into the cavity of the reactive plasma deposition equipment, and the flow rate of the introduced oxygen is reduced from 40sccmThe step length of 5sccm is reduced to 5sccm, and the value range of the background vacuum of the reactive plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
7. The method of claim 2, wherein the fabricating the second ohmic contact layer using a reactive plasma deposition process comprises:
preparing a second ohmic contact layer with the thickness of 20-100 angstroms under a fifth preset condition;
the fifth preset condition includes: argon gas with the flow rate of 70-80 sccm is introduced through a reaction ion gun of the reaction plasma deposition equipment, the value of the current of a magnetic coil of the reaction plasma deposition equipment is controlled within the range of 50-75A, target process gas is introduced into a cavity of the reaction plasma deposition equipment, the target process gas comprises oxygen with the flow rate of 0-5 sccm and argon gas with the flow rate of 40-60 sccm, and the value range of background vacuum of the reaction plasma deposition equipment is 1.0 multiplied by 10-6～1.0×10-3Pa, and the value range of the cavity temperature of the reactive plasma deposition equipment is 65-90 ℃.
8. The method of claim 2, wherein after the fabricating the first functional layer using a reactive plasma deposition process, prior to the fabricating the current conducting layer using a reactive plasma deposition process further comprises:
and carrying out primary annealing treatment on the substrate and the surface film layer thereof, wherein the temperature range of the primary annealing treatment is 250-350 ℃, and the annealing time range is 5-15 min.
9. The method of claim 2, wherein after the fabricating the current conducting layer using a reactive plasma deposition process, prior to the fabricating the second functional layer using a reactive plasma deposition process further comprises:
and carrying out secondary annealing treatment on the substrate and the surface film layer thereof, wherein the temperature range of the secondary annealing treatment is 250-350 ℃, and the annealing time range is 5-15 min.
10. The method of claim 1, wherein after providing the substrate, the method further comprises, before sequentially forming a first ohmic contact layer, a first functional layer, a current conducting layer, a second functional layer, and a second ohmic contact layer on the surface of the substrate by using a reactive plasma deposition process:
placing the substrate into a cavity of a reactive plasma deposition device for preheating treatment, wherein the temperature of the cavity ranges from 100 to 200 ℃ during preheating treatment, the preheating time ranges from 15 to 50min, and the background vacuum ranges from 2.0 x 10-4～3.0×10-4Pa。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011181803A (en) * | 2010-03-03 | 2011-09-15 | Fujifilm Corp | Method of manufacturing igzo-based amorphous oxide thin film and method of manufacturing field effect transistor using the same |
| CN108493105A (en) * | 2018-02-26 | 2018-09-04 | 清华大学 | Silica membrane and preparation method thereof |
| CN208078005U (en) * | 2018-02-02 | 2018-11-09 | 大连德豪光电科技有限公司 | A kind of LED chip improving external quantum efficiency |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7176111B2 (en) * | 1997-03-28 | 2007-02-13 | Interuniversitair Microelektronica Centrum (Imec) | Method for depositing polycrystalline SiGe suitable for micromachining and devices obtained thereof |
| US6716476B2 (en) * | 2001-09-21 | 2004-04-06 | Dalsa Semiconductor Inc. | Method of depositing an optical quality silica film by PECVD |
| TW201112424A (en) * | 2009-09-16 | 2011-04-01 | Archers Systems Inc | Thin film solar cell and method of forming the same |
| TWI395352B (en) * | 2010-02-09 | 2013-05-01 | Epistar Corp | Optoelectronic device and the manufacturing method thereof |
| CN102623589B (en) * | 2012-03-31 | 2014-08-13 | 厦门市三安光电科技有限公司 | Manufacturing method of semiconductor light-emitting device with vertical structure |
| JP6146160B2 (en) * | 2013-06-26 | 2017-06-14 | 東京エレクトロン株式会社 | Film forming method, storage medium, and film forming apparatus |
| CN105304510B (en) * | 2014-07-22 | 2018-05-08 | 北京北方华创微电子装备有限公司 | Aluminium film preparation method |
| CN107731969A (en) * | 2017-10-18 | 2018-02-23 | 湘能华磊光电股份有限公司 | The preparation method of LED chip |
| US10975464B2 (en) * | 2018-04-09 | 2021-04-13 | International Business Machines Corporation | Hard mask films with graded vertical concentration formed using reactive sputtering in a radio frequency deposition chamber |
| CN109182971B (en) * | 2018-07-11 | 2020-02-07 | 南开大学 | Method for growing wide-spectrum MGZO-TCO film by using reactive plasma deposition technology and application |
| CN110190160B (en) * | 2019-06-14 | 2020-11-20 | 江西乾照光电有限公司 | Low-defect-density LED epitaxial structure and manufacturing method thereof |
| CN211455715U (en) * | 2020-03-06 | 2020-09-08 | 厦门乾照半导体科技有限公司 | High-reflection LED flip chip and packaging structure thereof |
| CN112038455B (en) * | 2020-08-27 | 2021-12-31 | 厦门士兰明镓化合物半导体有限公司 | Ultraviolet light emitting diode and manufacturing method thereof |
-
2021
- 2021-01-20 CN CN202110075647.0A patent/CN112885718B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011181803A (en) * | 2010-03-03 | 2011-09-15 | Fujifilm Corp | Method of manufacturing igzo-based amorphous oxide thin film and method of manufacturing field effect transistor using the same |
| CN208078005U (en) * | 2018-02-02 | 2018-11-09 | 大连德豪光电科技有限公司 | A kind of LED chip improving external quantum efficiency |
| CN108493105A (en) * | 2018-02-26 | 2018-09-04 | 清华大学 | Silica membrane and preparation method thereof |
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