CN108251811A - In2(SxSe1-x)3The preparation method of thin-film material - Google Patents

In2(SxSe1-x)3The preparation method of thin-film material Download PDF

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CN108251811A
CN108251811A CN201810062500.6A CN201810062500A CN108251811A CN 108251811 A CN108251811 A CN 108251811A CN 201810062500 A CN201810062500 A CN 201810062500A CN 108251811 A CN108251811 A CN 108251811A
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target
targets
thin
film material
preparation
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刘芳洋
康亮亮
翁娜娜
蒋良兴
李靖
张阳
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Central South University
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Central South University
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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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • 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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623—Sulfides, selenides or tellurides
    • 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
    • C23C14/58—After-treatment
    • C23C14/5873—Removal of material

Abstract

The invention discloses a kind of In2(SxSe1‑x)3The preparation method of thin-film material, the In2(SxSe1‑x)3The preparation method of thin-film material includes：The first step carries out cleaning treatment to substrate surface；Second step, substrate surface after the cleaning process deposit In by one step of Magnetron reactive sputtering2(SxSe1‑x)3Film, wherein, 0≤x≤1；Third walks, to In2(SxSe1‑x)3Film surface performs etching processing.In proposed by the present invention2(SxSe1‑x)3The preparation method of thin-film material has many advantages, such as at low cost, the easily-controllable adjustable, favorable reproducibility of thin film composition and suitable film large area deposition, and prepared film has good ingredient controllability and uniformity, superior crystalline quality and translucency.

Description

In2(SxSe1-x)3The preparation method of thin-film material
Technical field
The present invention relates to optoelectronic materials technology more particularly to a kind of In2(SxSe1-x)3The preparation method of thin-film material.
Background technology
Present Global energy crisis and atmosphere polluting problem become increasingly conspicuous, and sight is all invested regenerative resource by the whole world, Wherein solar energy is with its exclusive advantage and as people's focus of attention.Abundant solar radiant energy is important the energy, takes Not to the utmost, it is nexhaustible, be the energy that the mankind can freely utilize.There are mainly three types of the direct Land use systems of solar energy：Photo-thermal Conversion, photochemical transformation and opto-electronic conversion.Solar water heating system is the typical case of photothermal conversion, extensively should at present With.Photochemical convertion is substantially at laboratory stage, than it is more typical be exactly photochemistry hydrogen manufacturing.Photoelectric conversion is then solar energy profit With one of most important direction, main forms are photovoltaic generation.
Under the inflection point of current China's economic restructure, photovoltaic generation will welcome new technological progress and industry increases, and make For a kind of new energy using solar energy, do not need to compete the resources such as oil, coal as traditional energy, but be embodied in To in the demand of core technology.Just on April 19th, 2016, National Development and Reform Committee and Bureau of Energy have issued new energy technology leather jointly Life innovation action plan (2016-the year two thousand thirty) and energy technology revolution emphasis innovation course of action figure, show what the energy was reformed The attention being determined with technological innovation.Main body of the solar cell as photovoltaic generation, production cost and transfer efficiency determine should With value.At present, as the crystal silicon solar battery of the market mainstream, technology development space is being gradually reduced, and does not have still There are the stage for reaching and maintaining an equal level with fossil fuel power cost, therefore the inexpensive battery material of Development of Novel and suitable preparation Technology is necessary.
In solar cell, the band gap width in many cases between Window layer and absorbed layer is larger.Therefore, it is absorbing Layer adds a buffer layer to complete the energy transition among absorbed layer and Window layer with Window layer intermediate demand, reduces the two Between band gap step and lattice mismatch, adjust conduction band side imbalance value.This can play improvement pn-junction quality and battery performance important Effect.Therefore it chooses appropriate cushioning layer material, prepare the buffer layer of preferable pattern for preparing efficient solar cell particularly It is important.
In past research, CdS is that have the cushioning layer material for meeting requirement on devices performance, however Cd is as a kind of Toxic element, and sustainable development idea is not met, therefore suitable alternative materials In should be selected2(SxSe1-x)3It is to compare One of ideal alternative materials.
In2(SxSe1-x)3The preparation method of thin-film material is generally using chemical bath method, Co-evaporated Deposition method, chemical spray Then pyrolysismethod carries out the high temperature anneal under the atmosphere of sulfur-bearing or selenium.The reaction of chemical bath method is complex, it is difficult to accurate Film composition is controlled, deposition rate is also relatively slow, and is difficult to large area production and promotes.Chemical spray pyrolysismethod is asked there are following Topic：Impurity residual that organic matter volatile zone comes, the generation of pore, toxic and high cost organic matter use, thickness, adhesive force and Ingredient is difficult to control.Co-evaporated Deposition method due to the difference of different materials saturated vapor pressure, the evaporation rate of different evaporation sources and Evaporation capacity is difficult to accurately control, thus is difficult to ensure that large area into film uniformity when preparing multi-element film.
Invention content
It is a primary object of the present invention to provide a kind of In2(SxSe1-x)3The preparation method of thin-film material, it is intended to solve existing There is method to prepare In2(SxSe1-x)3It is existing during thin-film material that ingredient is difficult to control, uniformity is not good enough, surface defect is more And the technical issues of being also easy to produce unfavorable dephasign.
To achieve the above object, In provided by the invention2(SxSe1-x)3The preparation method of thin-film material includes：
The first step carries out cleaning treatment to substrate surface；
Second step, substrate surface after the cleaning process deposit In by one step of Magnetron reactive sputtering2(SxSe1-x)3It is thin Film, wherein, 0≤x≤1；
Third walks, to In2(SxSe1-x)3Film surface performs etching processing.
Preferably, in the second step, the cathode target used is indium source target and/or chalcogen target.
Preferably, in the second step, the power supply that the cathode target uses is DC power supply or radio-frequency power supply.
Preferably, as x=0, indium source target is In targets, In2Se3Any one of target or In-Se alloys targets, institute Chalcogen target is stated as Se targets, In2Se3Any one of target or In-Se alloys targets；When 0<x<When 1, indium source target is In Target, In2S3Target, In2Se3Target, In2(SxSe1-x)3Appointing in target, In-S alloys targets, In-Se alloys targets or In-S-Se alloys targets It is a kind of；The chalcogen target is S targets, Se targets, In2S3Target, In2Se3Target, In2(SxSe1-x)3Target, SxSe1-xTarget, S-Se targets, Any one of In-S alloys targets, In-Se alloys targets or In-S-Se alloys targets；As x=1, indium source target for In targets, In2S3Any one of target or In-S alloys targets, the chalcogen target is S targets, In2S3Or any one of In-S alloys targets.
Preferably, as x=1, the sputter gas that uses is the mixed gas of hydrogen sulfide and argon gas；As x=0, use Mixed gas of the sputter gas for hydrogen selenide and argon gas；When 0<x<When 1, the sputter gas used is in hydrogen sulfide or hydrogen selenide At least one and argon gas mixed gas.
Preferably, argon gas flow is 1~1000sccm, hydrogen sulfide and hydrogen selenide gas flow be 1~ 1000sccm, sputtering intraventricular pressure is by force for 0.05Pa~15Pa, and the distance of target and base material is 3~18cm, the sputtering work(of cathode target Rate density is 0.5~100W/cm2, sedimentation time is 1~300min, and base material temperature is 30~700 DEG C, and with 1~1000r/ The rate of min rotates the base material.
Preferably, obtained In2(SxSe1-x)3The atomic percent of thin-film material is 0.5<In/(S+Se)<0.8.
Preferably, the third step includes：
Using KCN solution, deionized water or alkaline solution to In2(SxSe1-x)3Film surface performs etching processing；
Using deionized water to In after etching processing2(SxSe1-x)3Film surface is cleaned successively and drying and processing.
Preferably, the technological parameter of the etching processing is：
The mass percent concentration of KCN solution be 0.5%~50%, etch period be 1~100min, temperature for 15 DEG C~ 85℃；Alternatively,
Deionized water etch period is 1~100min, and temperature is 15 DEG C~90 DEG C；Alternatively,
The mass percent concentration of aqueous slkali is 0.1%~50%, 0.5~80min of etch period, and temperature is 15 DEG C~80 DEG C, wherein aqueous slkali is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or ammonium hydroxide.
In technical solution proposed by the present invention, In is formed using indium source target, chalcogen target, sputter gas reactive sputtering2 (SxSe1-x)3Thin-film material, this material are smooth by etching processing rear surface densification.This method can realize ingredient arbitrary proportion Regulation and control, and In obtained2(SxSe1-x)3Thin-film material crystallite dimension is 1~2 μm, and electrical and optical performance meets film too The requirement of buffer layer in positive energy cell photoelectric converting material.Compared with the preparation method of conventional solar cell buffer layer thin film, Since the material purity of reactive sputtering is high, be conducive to prepare high-purity compound film, and can a step to obtain Elemental redistribution equal It is even, fully and the excellent film of crystallization, in addition, the stoicheiometry of film is also easy to, to substrate material without particular/special requirement, easily In large-scale production.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention, for those of ordinary skill in the art, without creative efforts, can be with Structure according to these attached drawings obtains other attached drawings.
Fig. 1 is the SEM figures of indium sulfide thin film obtained in embodiment 1；
Fig. 2 is the band gap diagram of indium sulfide thin film obtained in embodiment 1；
Fig. 3 is the SEM figures of indium sulfide thin film obtained in embodiment 2；
Fig. 4 is the XRD diagram of indium sulfide thin film obtained in embodiment 2；
Fig. 5 is the transmitance figure of indium sulfide thin film obtained in embodiment 2.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete Site preparation describes, it is clear that described embodiment is only the part of the embodiment of the present invention, instead of all the embodiments.Base Embodiment in the present invention, those of ordinary skill in the art obtained without creative efforts it is all its His embodiment, shall fall within the protection scope of the present invention.
Embodiment 1
Step S100 vulcanizes by being formed on pretreated soda-lime glass by one step of DC magnetron reactive sputtering technique Indium film, at this time x=1.
Specifically, technological parameter is：Argon gas flow 8sccm, hydrogen sulfide gas flow 900sccm, when sputtering, sputter Indoor pressure is 0.8Pa, and the distance between target and soda-lime glass are 8cm, and cathode target uses indium target, and the sputtering power of indium target is close It spends for 10W/cm2, the temperature of soda-lime glass is 200 DEG C, and rotated with the rate of 25r/min, reaction time 250min.
It should be noted that one step of reactive sputtering deposits In2(SxSe1-x)3During film, in addition to indium target, indium source can be with It comes from：In2S3Target, In2Se3Target, In2(SxSe1-x)3(0≤x≤1) target, In-S (0<In/S<100) alloys target, In-Se (0< In/Se<100) alloys target or In-S-Se (0<In/(S+Se)<100；0<S/Se<100) any one of alloys target；Sulphur source or Selenium source could also be from chalcogen target, such as S targets, Se targets In2S3Target, In2Se3Target, In2(SxSe1-x)3Target, SxSe1-xTarget, Any one of S-Se targets, In-S alloys targets, In-Se alloys targets or In-S-Se alloys targets.
In the present embodiment, base material uses soda-lime glass, but base material is not limited only to soda-lime glass, can also use stainless Steel disc, copper sheet, FTO glass, ito glass and Mo glass etc..Mainly by the method for burn into cleaning and drying to the table of base material Face is pre-processed.
Step S200 performs etching indium sulfide thin film material processing, obtains the finished product of indium sulfide thin film material.
Specifically, etching processing uses mass percent concentration as 2.5% alkaline KCN solution, time 40min, temperature Spend is 45 DEG C.
Indium sulfide thin film material thickness made from the present embodiment is 50nm, with glass baseplate interface without cavity, SEM patterns without Hole, big crystal grain please refer to Fig. 1.And indium sulfide thin film material made from the above method is direct band gap, conduction type is N-shaped, Band gap width (Energy gap, Eg) is 2.62eV, please refers to Fig. 2.
It should be noted that the technological parameter by adjusting sputtering so that the ingredient of the finished product of indium sulfide thin film material is 0.5<In/S(Se)<When 0.8, be conducive to obtain larger crystallite dimension and better photoelectric properties.
Embodiment 2
Step S101 vulcanizes by being formed on pretreated soda-lime glass by one step of RF-reactive magnetron sputtering Indium film.
Specifically, technological parameter is：Argon gas flow 100sccm, hydrogen sulfide gas flow 5sccm, when sputtering, sputter Indoor pressure is 0.5Pa, and the distance of target and soda-lime glass is 10cm, and cathode target uses In2S3Target, In2S3The sputtering power of target Density is 82W/cm2, the temperature of soda-lime glass is 700 DEG C, and rotated with the rate of 150r/min, reaction time 10min.
Step S201 performs etching indium sulfide thin film material processing, obtains the finished product of indium sulfide thin film material.
Specifically, lithographic method is solution etches, and deionized water, KCN solution or aqueous slkali can be used, and certain in solution Solution temperature under film is performed etching, etch period is different according to different solutions and solution temperature.In the present embodiment, Etching processing uses mass percent concentration as 35% alkaline KOH solution, time 2.5min, and temperature is 76 DEG C.
The conduction type of indium sulfide thin film material made from the present embodiment is p-type, and band gap width 2.50eV, thickness is 50nm, with glass baseplate interface without cavity, SEM patterns please refer to Fig. 3 without hole, big crystal grain.In addition, according to Scherrer formula, It is 2.25 μm to calculate crystallite dimension.Moreover, please referring to Fig. 4, the indium sulfide thin film object that can be known is mutually very pure.It please refers to Fig. 5, after testing, indium sulfide thin film are about 90% to the transmitance of the light of 550-900nm ranges, meet solar cell buffer layer Material requirements.
Embodiment 3
Step S102, by passing through double target response cosputtering depositing indium sulfide thin films on pretreated soda-lime glass.
Specifically, technological parameter is：Argon gas flow 80sccm, hydrogen sulfide gas flow 90sccm, when sputtering, sputter Indoor pressure is 12Pa, and the distance of target and soda-lime glass is 16cm, and cathode target uses In-S alloys targets and S targets, In-S alloys The Sputtering power density of target is 5W/cm2, the Sputtering power density of S alloys targets is 25W/cm2, the temperature of soda-lime glass is 400 DEG C, And it is rotated with the rate of 180r/min, reaction time 200min.
Step S202 forms indium sulfide thin film material to reaction cosputtering and performs etching processing, obtains indium sulfide thin film material The finished product of material.
Specifically, etching processing uses mass percent concentration the time is for 5% NaOH and 12%KCN solution 10min, temperature are 60 DEG C.
The conduction type of indium sulfide thin film material made from the present embodiment is N-shaped, and band gap width 2.40eV, thickness is 80nm, with glass baseplate interface without cavity, it is 1.5 μm to calculate crystallite dimension according to Scherrer formula.
Embodiment 4
Step S103 deposits indium selenide films on pretreated soda-lime glass is passed through using double target response cosputterings, X=0 at this time.
Specifically, technological parameter is：Argon gas flow 40sccm, hydrogen selenide gas flow 25sccm, when sputtering, sputter Indoor pressure is 0.8Pa, and the distance of target and soda-lime glass is 8cm, and cathode target uses In-Se alloys targets and In2Se3Target makes With radio-frequency power supply, the Sputtering power density of In-Se alloys targets is 12W/cm2, In2Se3The Sputtering power density of target is 8W/cm2, The temperature of soda-lime glass is 600 DEG C, and with the rate rotation of 200r/min, reaction time 30min.
Step S203, the indium sulfide thin film material formed to reaction cosputtering perform etching processing, obtain indium sulfide thin film The finished product of material.
Specifically, etching processing uses mass percent concentration as 25% alkaline KCN solution, time 5min, temperature It is 60 DEG C.
The conduction type of indium selenide thin-film material made from the present embodiment is N-shaped, and band gap width 2.43eV, thickness is 40nm, with glass baseplate interface without cavity, it is 1 μm to calculate crystallite dimension according to Scherrer formula.
Embodiment 5
Step S104, by thin using double target response cosputtering SEDIMENTARY SELENIUM indium sulfides on pretreated soda-lime glass Film, at this time 0<x<1.
Specifically, technological parameter is：Argon gas flow 40sccm, hydrogen selenide gas flow 125sccm, when sputtering, sputter Indoor pressure is 1.8Pa, and the distance of target and soda-lime glass is 12cm, and cathode target uses In-Se-S alloys targets and S-Se targets, Using radio-frequency power supply, the Sputtering power density of In-Se-S alloys targets is 20W/cm2, the Sputtering power density of S-Se targets is 8W/ cm2, the temperature of soda-lime glass is 600 DEG C, and rotated with the rate of 200r/min, reaction time 30min.
Step S204, the selenium indium sulfide thin film material formed to reaction cosputtering perform etching processing, obtain selenium indium sulfide The finished product of thin-film material.
Specifically, etching processing uses mass percent concentration as 45% alkaline KCN solution, time 10min, temperature It is 25 DEG C.
The conduction type of selenium indium sulfide thin film material made from the present embodiment is N-shaped, and band gap width 1.90eV, thickness is 90nm, with glass baseplate interface without cavity, it is 1 μm to calculate crystallite dimension according to Scherrer formula.
Embodiment 6
Step S105, by thin using double target response cosputtering SEDIMENTARY SELENIUM indium sulfides on pretreated soda-lime glass Film.
Specifically, technological parameter is：Argon gas flow 60sccm, hydrogen selenide gas flow 300sccm, when sputtering, sputter Indoor pressure is 0.45Pa, and the distance of target and soda-lime glass is 12cm, and cathode target uses In2(SxSe1-x)3Target and S-Se targets, Using radio-frequency power supply, In2(SxSe1-x)3The Sputtering power density of target is 10W/cm2, the Sputtering power density of S-Se targets is 18W/cm2, the temperature of soda-lime glass is 600 DEG C, and rotated with the rate of 10r/min, reaction time 45min.
Step 205, selenium indium sulfide thin film material is formed to reaction cosputtering and performs etching processing, obtain selenium indium sulfide thin film The finished product of material.
Specifically, etching processing uses mass percent concentration as 15% alkaline KCN solution, time 20min, temperature It is 55 DEG C.
The conduction type of selenium indium sulfide thin film material made from the present embodiment is p-type, and band gap width 1.80eV, thickness is 100nm, with glass baseplate interface without cavity, it is 1.8 μm to calculate crystallite dimension according to Scherrer formula.
The foregoing is merely the preferred embodiment of the present invention, are not intended to limit the scope of the invention, every at this Under the design of invention, the equivalent structure transformation made using description of the invention and accompanying drawing content or directly/be used in it indirectly His relevant technical field is included in the scope of patent protection of the present invention.

Claims (9)

1. a kind of In2(SxSe1-x)3The preparation method of thin-film material, which is characterized in that including：
The first step carries out cleaning treatment to substrate surface；
Second step, substrate surface after the cleaning process deposit In by one step of Magnetron reactive sputtering2(SxSe1-x)3Film, In, 0≤x≤1；
Third walks, to In2(SxSe1-x)3Film surface performs etching processing.
2. In as described in claim 12(SxSe1-x)3The preparation method of thin-film material, which is characterized in that in the second step, The cathode target used is indium source target and/or chalcogen target.
3. In as claimed in claim 22(SxSe1-x)3The preparation method of thin-film material, which is characterized in that in the second step, The power supply that the cathode target uses is DC power supply or radio-frequency power supply.
4. In as claimed in claim 22(SxSe1-x)3The preparation method of thin-film material, which is characterized in that described as x=0 Indium source target is In targets, In2Se3Any one of target or In-Se alloys targets, the chalcogen target is Se targets, In2Se3Target or Any one of In-Se alloys targets；When 0<x<When 1, indium source target is In targets, In2S3Target, In2Se3Target, In2 (SxSe1-x)3Any one of target, In-S alloys targets, In-Se alloys targets or In-S-Se alloys targets；The chalcogen target is S targets Material, Se targets, In2S3Target, In2Se3Target, In2(SxSe1-x)3Target, SxSe1-xTarget, S-Se targets, In-S alloys targets, In-Se alloys targets Or any one of In-S-Se alloys targets；As x=1, indium source target is In targets, In2S3In target or In-S alloys targets Any, the chalcogen target is S targets, In2S3Or any one of In-S alloys targets.
5. such as claim 2-4 any one of them In2(SxSe1-x)3The preparation method of thin-film material, which is characterized in that work as x= When 1, the sputter gas that uses is the mixed gas of hydrogen sulfide and argon gas；As x=0, the sputter gas that uses for hydrogen selenide and The mixed gas of argon gas；When 0<x<When 1, the sputter gas that uses is at least one of hydrogen sulfide or hydrogen selenide and argon gas Mixed gas.
6. In as claimed in claim 52(SxSe1-x)3The preparation method of thin-film material, which is characterized in that argon gas flow For 1~1000sccm, hydrogen sulfide and hydrogen selenide gas flow are 1~1000sccm, sputtering intraventricular pressure by force for 0.05Pa~ The distance of 15Pa, target and base material is 3~18cm, and the Sputtering power density of cathode target is 0.5~100W/cm2, sedimentation time is 1~300min, base material temperature are 30~700 DEG C, and rotate the base material with the rate of 1~1000r/min.
7. In as described in claim 12(SxSe1-x)3The preparation method of thin-film material, which is characterized in that obtained In2 (SxSe1-x)3The atomic percent of thin-film material is 0.5<In/(S+Se)<0.8.
8. In as described in claim 12(SxSe1-x)3The preparation method of thin-film material, which is characterized in that the third step packet It includes：
Using KCN solution, deionized water or alkaline solution to In2(SxSe1-x)3Film surface performs etching processing；
Using deionized water to In after etching processing2(SxSe1-x)3Film surface is cleaned successively and drying and processing.
9. In as claimed in claim 82(SxSe1-x)3The preparation method of thin-film material, which is characterized in that the etching processing Technological parameter be：
The mass percent concentration of KCN solution is 0.5%~50%, and etch period is 1~100min, and temperature is 15 DEG C~85 ℃；Alternatively,
Deionized water etch period is 1~100min, and temperature is 15 DEG C~90 DEG C；Alternatively,
The mass percent concentration of aqueous slkali is 0.1%~50%, 0.5~80min of etch period, and temperature is 15 DEG C~80 DEG C, Wherein aqueous slkali is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or ammonium hydroxide.
CN201810062500.6A 2018-01-23 2018-01-23 In2(SxSe1-x)3The preparation method of thin-film material Pending CN108251811A (en)

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JP2017014599A (en) * 2015-07-06 2017-01-19 三菱マテリアル株式会社 Sputtering target and production method thereof
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