CN104701413A - Large-area cadmium sulfide film preparing method - Google Patents
Large-area cadmium sulfide film preparing method Download PDFInfo
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- CN104701413A CN104701413A CN201410532490.XA CN201410532490A CN104701413A CN 104701413 A CN104701413 A CN 104701413A CN 201410532490 A CN201410532490 A CN 201410532490A CN 104701413 A CN104701413 A CN 104701413A
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Abstract
Disclosed is a large-area cadmium sulfide film preparing method which is implemented in the presence of high ammonia by a chemical immersion method on the basis of a copper-indium-gallium-selenium substrate. The large-area cadmium sulfide film preparing method is characterized by including the steps of preparing a molybdenum electrode on a glass substrate by a magnetron sputtering method, preparing a copper-indium-gallium-selenium film by a co-evaporation method, preparing a large-area CdS (cadmium sulfide) film on the surface of a composite substrate by the chemical immersion method under a high-ammonia condition. The large-area cadmium sulfide film preparing method which is implemented in the presence of high ammonia by the chemical immersion method on the basis of the copper-indium-gallium-selenium substrate has the advantages of good crystallization quality, high density and no pin hole in crystallization, good repeatability, high efficiency in deposition of a large-area cadmium sulfide film, good crystal adhesiveness, high crystal transmittance, simplicity, easiness in implementation, benefit to large-scale popularization and application and vitally important application prospect in industrial production.
Description
Technical field
The present invention relates to thin film solar cell technical field, particularly in the thin film solar cell field taking Copper Indium Gallium Selenide as absorbed layer, cadmium sulphide membrane can regulate band gap gradient as crucial one deck as resilient coating and as n-type semiconductor.
Background technology
Cadmium sulfide (CdS) a kind ofly has research potential and the semi-conducting material utilizing form wide, and it is easy to prepare, the high and applicable large-scale production of cost performance.Cadmium sulfide also has and multiplely utilizes form in addition.It can be made into, as the zero dimension such as elementide, nano particle material, can be used for preparing multiple quantum device; Can be prepared to as monodimension nanometer materials such as nano wire, nanometer rods, nano flower, nanobelt, nano-hollow balls, can be applicable to nanowire lasers, gate counting circuit, nanowire sensor, P-N save diode and inverter etc.; Also can be prepared to the two-dimension nano materials as superlattice, multilayer film and ultrathin membrane etc., be mainly used to as photoconductive device, window material etc.In addition, cadmium sulfide also can be applicable to holder, photochemical catalysis, electrode material, high-resolution display, imageing sensor, light sensor and utilizes the thermal infrared transparency as the special antiradar coatings etc. of pigment doping.CdS semiconduct material has broad application prospects in the energy, catalysis, electronics, medical treatment, national defence, Industry Control, Robotics and biotechnology field.
No matter at Copper Indium Gallium Selenide (CIGS) or cadmium telluride (CdTe) battery, cadmium sulfide is all very crucial one deck.In cadmium telluride cells, cadmium sulfide is as n-type semiconductor, in CIGS thin film solar cell, cadmium sulfide is as the key stratum of resilient coating between Copper Indium Gallium Selenide and zinc oxide (ZnO), on the one hand as n-type semiconductor, Copper Indium Gallium Selenide and zinc oxide band gap gradient can be regulated on the other hand.Transparent in cadmium sulphide membrane that is high resistivity in order to prepare, develop a variety of method and prepare.As chemical vapour deposition (CVD) (CVD), plating, rf magnetron sputtering, chemical bath method.
Current immersion method is prepared cadmium sulfide and is considered to most prospect.Its reaction comprises two parts: 1. between isolated ion, chemical reaction occurs.2. the micel accumulation process of reaction generation.
In CIGS solar cell and copper zinc selenium sulfur solar cell, cadmium sulphide membrane is all very crucial one deck.And the cadmium sulphide membrane preparing free of pinholes generally uses chemical bath (CBD) method, prepared film and Copper Indium Gallium Selenide lattice mismatch less.There being the method for the high ammonia using buffer for cadmium sulphide membrane by chemical bath legal system, also there is the method for the high ammonia not using buffer.High ammonia process can use less ammoniacal liquor raw material, and reduce environmental pollution, and preparing in resilient coating cadmium sulfide process because it is very crucial for controlling ammonia vol with immersion method, especially the control preparing cadmium sulfide ammonia vol at high ammonia process is the key preparing cadmium sulphide membrane, because ammoniacal liquor is very few can not be deposited as film, ammonia vol is too high, and precipitation can occur affects film quality and even can not be deposited as film.
Summary of the invention
In view of this, for overcoming the deficiencies in the prior art, the invention provides one and prepare scheme based on Copper Indium Gallium Selenide substrate with high ammonia process, first washed with de-ionized water Copper Indium Gallium Selenide substrate surface is used then at its surface deposition one deck cadmium sulphide membrane, finally can prepare zinc oxide and native oxide zinc above, finally prepare nickel aluminium electrode and obtain battery component.This kind is good with the cadmium sulphide membrane crystalline quality prepared under chemical bath method height ammonia condition, and the few and fine and close free of pinholes of defect, transmitance is high.
Technical scheme of the present invention:
A kind of preparation process of the thin film solar cell film absorption layer based on Copper Indium Gallium Selenide substrate is as follows: first will prepare preparation Mo electrode on a glass substrate and then prepare CIGS thin film
The preparation of molybdenum back contact
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the Mo of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit the molybdenum film of one deck high resistant and low-resistance respectively at substrate surface.1. base vacuum: 3.0-3.2 × 10
-4pa, operating air pressure is 0.5-1Pa, and underlayer temperature is room temperature 25-30 DEG C, and radio-frequency power is 500-600W, Ar throughput is 35-40sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 2 times.2. operating air pressure is 0.1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 1500W, Ar throughput is 15sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 6 times.
The preparation process of CIGS thin film is as follows:
1) base vacuum is 4.4 × 10
-4pa, underlayer temperature is 400 DEG C, and coevaporation In, Ga, Se initialization layer is about 5min, and wherein In source temperature is 850-900 DEG C, Ga source temperature be 880-920 DEG C, Se source temperature is 450-500 DEG C, and evaporation time is 15-20min.
2) underlayer temperature is 500-550 DEG C, coevaporation Cu, Se, and wherein Cu source temperature is 1140-1160 DEG C, Se source temperature is 240-280 DEG C, and evaporation time is 20-30min;
3) what underlayer temperature kept in second step is temperature-resistant, coevaporation In, Ga, Se, wherein In source temperature is 850-900 DEG C, Ga source temperature is 880-920 DEG C, Se source temperature is 240-280 DEG C, evaporation time is 2-4min, and obtain the Copper Indium Gallium Selenide p-type yellow copper structure of poor a little Cu, control Cu/ (In+Ga) ratio is at 0.88-0.92.
4) substrate being cooled, when evaporating underlayer temperature when substrate to be cooled to while Se the first step, closing Se evaporation source, then by substrate cool to room temperature.
Under use chemical bath method height ammonia condition, the preparation process of cadmium sulfide resilient coating is as follows:
(1) dosing, use cadmium acetate is cadmium salt, and ammonium acetate is buffer, and thiocarbamide is sulphur source, wiring solution-forming: (CH3COO)
2in order to be made into 0.05M, to get amount of medicament be 26.652g, CH to Cd
3cOONH
4to get it filled product 23.124g, SC (NH2) to be made into 0.15M
2to get it filled product 23.124g for being made into 0.5M, the deionized water and stirring adding 2L is even.By (CH3COO) of 2L
2cd solution mark becomes No. 1 liquid, by CH
3cOONH
4with SC (NH
2)
2mixed type 2L solution mark become No. 2 liquid.
(2) get reagent and regulate ratio of reagents: No. 1 liquid uses 20-25mL, and No. 2 liquid are got containing NH with 25-30mL at every turn at every turn
3quality proportion is the ammoniacal liquor 37.5-40mL of 25%-28%, puts into the beaker of a 2L, add deionized water be diluted to 1L stir 5min then put into 2L beaker.
(3) sample is placed: size CIGS sample substrate being tailored into 10cm × 10cm, clamp with sawtooth frame in the middle of the beaker put into and be furnished with solvent, samples vertical is put vertical (as shown in Figure 1).
(4) reactive deposition growth: put into water-bath by what be equipped with sample and solvent from beaker, water-bath will be warmed up to 70-80 DEG C in advance.Initial reaction stage phase solution is transparent, uses magnetic rotor in early stage, and rotor speed control is at 140-150 rev/min (r/min), and after wait 10min-15min, solution colour becomes muddy, and now stopping rotor should timing 20-30min.
(5) sample takes out and cleaning: take out sample after becoming muddy rear timing to 20-30min, and with deionized water rinsing, but due to prepared cadmium sulfide be comprise same qualitative response and heterogeneous response competition reaction prepared by film, because surface has a small amount of precipitation to affect film quality, so 2L beaker should be put into add 1.8L deionized water use Ultrasonic Cleaning, ultrasonic frequency is 20-25Hz, takes out sample after Ultrasonic Cleaning 20-25min, uses nitrogen to dry up.
Principle analysis of the present invention:
In order to meet, to prepare crystalline quality better, transmitance is high, and the film requirement good with Copper Indium Gallium Selenide substrate adhesion, ammonia vol and Temperature Matching must be made to ensure, and with qualitative response and heterogeneous reaction, heterogeneous reaction in the process of competitive reaction occupies an leading position to obtain the cadmium sulphide membrane of the good fine and close free of pinholes of transmitance high tack.
It deposits three phases:
(1) bring out the stage (between AB section): now solute is hydrolyzed in the solution, does not react
(2) growth phase (between BC section): this stage film is mainly with heterogeneous reaction growth (between ion and ion reaction growth), and comparatively even compact is without cavity for the film of this phase deposition, and tack is good.
(3) saturation stage (between CD section): this stage film is mainly with same qualitative response growth (micel gathering is adsorbed on sample surfaces), and the uniformity of film of this phase deposition is poor, and has cavity, and tack is poor.
So generally reaction controlling is obtained the comparatively good film of even compact tack in the BC stage with CBD method deposit film.
Growth rate comparatively low reaction nucleation in the process of first step growth.Grow by steady rate when second step reacts, this reaction mechanism is ion and ionic reaction growth, becomes film when Cd2+ with S2-reacts in superficial growth.Generate complex compound in surface adhesion simultaneously.3rd step generates the less film of tack at Surface disintegration.
Reactional equation can split into following three steps, the process of release Cd2+, the process of release S2-.Last Cd2+ and S2-reaction generates CdS.
And in actual deposition growth CdS film process, wish that heterogeneous reaction i.e. (2) step reaction is much larger than (3) step reaction, the fine and close free of pinholes of the film that guarantee of occupying an leading position in whole growth course generates, tack is good and have good transmitance.
Large area is prepared in CdS process should consider that the impact of rotor on heterogeneous reaction comprises the absorption generation in room and the speed of deamination.Fig. 3 gives and add the impact of rotor on reaction three phases in different phase.(1), when a curvilinear surface does not add rotor stirring, front 20min is the stage of bringing out.Rear 60min is growth phase, is finally saturation stage.(2) b curve shortens to 15min for adding stirring (rotating speed the is 120r/min) stage of bringing out, mainly because cause heterogeneous reaction to be accelerated in the probability increase of heterogeneous course of reaction intermediate ion contact.(3) c curve is the solution (dilution is original 16/18) after dilution.Can find out that the stage of bringing out postpones as 25min.Because after dilution contacted with ions reaction probability reduce cause heterogeneous reaction slack-off caused by.
With CBD legal system for large-area CdS in must solve temperature gradient so will stir, can temperature gradient be eliminated when rotating speed is 120r/min.20min can reach design temperature 80 DEG C.And stirring can cause the stage of bringing out shorten reaction comparatively fast (only have 15min just to enter growth phase, this just means that temperature does not also reach design temperature and just enters growth phase), easily affect nucleation when growth phase adds stirring, film growth transmitance and thickness cannot ensure.So must stop stirring before growth phase.In order to unfavorable use of bringing out that phases-time shortens after making up stirring is reduced concentration and added the dilution of more deionized water for original 16/18 and extend and bring out phases-time, stop after 20min stirring.Last just can meet can to reach when 20min eliminate temperature gradient on the one hand, another aspect can not cause bring due to whipping process affect ionic reaction in the nucleation of substrate surface and absorption.
Prepare large area cadmium sulphide membrane under using chemical bath method height ammonia condition based on Copper Indium Gallium Selenide substrate and prepare benefit analysis:
1) reaction temperature is low: it does not need the hot conditions required by other modes, avoids the corrosion of oxidation and metallic matrix, adds the alternative of substrate;
2) equipment is simple: it does not need complicated instrument and expensive equipment, such as vapour system, vacuum system etc.;
3) reaction raw materials purity requirement is lower: CBD does not require highly purified reaction raw materials, and this makes the source of raw material more extensive, and low price, easily buy;
4) filming performance is good: fine and close with the film of the method deposit, evenly, film functional;
5) CBD method can also realize single, repeatedly or successive sedimentation film.
6) ammonia vol is higher, prepared CdS film repeatability feel better ammonia vol and PH restriction little.
7) owing to being large area preparation, average consumed raw material is little, and the few and plated film area of energy resource consumption strengthens.
Advantage of the present invention is: prepare the preparation of large area cadmium sulphide membrane under using chemical bath method height ammonia condition based on Copper Indium Gallium Selenide substrate and ensure that controllability is good, chemistry tolerance is high, reaction efficiency can obtain the CdS film of required thickness soon at short notice, CBD method is the technology of a kind of low production cost and low temperature depositing film, and is widely used in the research and preparation aspect of sulfur family II-VI group metallic compound and film thereof in recent years.At present, in the preparation of the resilient coating of CIGS solar cell and the Window layer of CdTe solar cell, CBD technology has become the method for its first-selection.
Accompanying drawing explanation
Accompanying drawing 1 prepares CdS film schematic diagram for use chemical bath method height ammonia condition based on CIGS solar cell substrate under.
Accompanying drawing 2 prepares CdS film SEM figure for use chemical bath method height ammonia condition in CIGS solar cell substrate under.(a in figure is the SEM exterior view amplifying 10K, and figure b is the SEM exterior view amplifying 50K).
Accompanying drawing 3 is that under different condition the stage of reaction is over time
CIGS solar battery structure schematic diagram prepared by accompanying drawing 4
Embodiment
In order to make those skilled in the art person understand the present invention program better, below in conjunction with drawings and embodiments, the present invention is described in further detail.
Embodiment 1:
Prepare the preparation of large area cadmium sulphide membrane under using chemical bath method height ammonia condition based on Copper Indium Gallium Selenide substrate, its preparation process is as follows:
The preparation of Copper Indium Gallium Selenide substrate: first will obtain CIGS absorbed layer prepared on a glass substrate.
1) cleaning of soda lemon glass
1. the soda glass of 10cm × 10cm is put in heavy hydrogen potassium oxide solution (by 300 grams of potassium hydroxide, the solution of 3 liters of deionized water configurations) and soak 2h; 2. be placed in rinsing clean soda glass the acetone soln that concentration is 99.5%, putting into supersonic wave cleaning machine, to clean ultrasonic frequency be 50kHz, and the time is 30min, can suitably be heated to be 40 DEG C; 3. soda glass is taken out from acetone soln, with deionized water rinsing; 4. then the soda lemon glass substrate alcohol washes washed is dried up with nitrogen.
2) preparation of molybdenum back contact
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the Mo of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit the molybdenum film of one deck high resistant and low-resistance respectively at substrate surface.1. base vacuum: 3.0 × 10
-4pa, operating air pressure is 1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 600W, Ar throughput is 40sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 2 times.2. operating air pressure is 0.1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 1500W, Ar throughput is 15sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 6 times.
3) preparation of CuInGaSe absorbed layer film
1. base vacuum is 4.0 × 10
-4pa, underlayer temperature is 500 DEG C, coevaporation In, Ga, Se initialization layer 2min, and wherein In source temperature is 800 DEG C, and Ga source temperature is 840 DEG C, and Se source temperature is 400 DEG C, and evaporation time is 20min; 2. underlayer temperature is 550 DEG C, coevaporation Cu, Se, and wherein Cu source temperature is 1200 DEG C, and Se source temperature is 250 DEG C, and evaporation time is 20min; What 3. underlayer temperature kept in second step is temperature-resistant, coevaporation In, Ga, Se, and wherein In source temperature is 850 DEG C, and Ga source temperature is 880 DEG C, and Se source temperature is 450 DEG C, and evaporation time is 5min; 4. substrate is cooled, when evaporate substrate to be cooled to while Se 400 DEG C time, close Se evaporation source, then substrate cool to room temperature can be obtained the CIGS thin-film in glass substrate.
4) preparation of cadmium sulfide buffer layer thin film
(1) dosing, use cadmium acetate is cadmium salt, and ammonium acetate is buffer, thiocarbamide is sulphur source, wiring solution-forming: to get amount of medicament be 26.652g to (CH3COO) 2Cd in order to be made into 0.05M, to get it filled product 23.124g for being made into 0.5M, the deionized water and stirring adding 2L is even.By (CH3COO) of 2L
2cd solution mark becomes No. 1 liquid, by SC (NH
2)
2the 2L solution mark be made into becomes No. 2 liquid.
(2) get reagent and regulate ratio of reagents: No. 1 liquid uses 20mL at every turn, it is the ammoniacal liquor 37.5mL of 25%-28% that No. 2 liquid is got containing NH3 quality proportion with 25-30mL at every turn, put into the beaker of a 2L, add deionized water be diluted to 1L stir 5min then put into 2L beaker.
(3) sample is placed: size CIGS sample substrate being tailored into 10cm × 10cm, clamp with sawtooth frame in the middle of the beaker put into and be furnished with solvent, samples vertical is put vertical (as shown in Figure 1).
(4) reactive deposition growth: put into water-bath by what be equipped with sample and solvent from beaker, water-bath will be warmed up to 75 DEG C in advance.Initial reaction stage phase solution is transparent, uses magnetic rotor in early stage, and rotor speed control is at 140 revs/min (r/min), and after wait 15min, solution colour becomes muddy, and now stopping rotor should timing 20min.
(5) sample takes out and cleaning: take out sample after becoming muddy rear timing to 20min, and with deionized water rinsing, but due to prepared cadmium sulfide be comprise same qualitative response and heterogeneous response competition reaction prepared by film, because surface has a small amount of precipitation to affect film quality, so 2L beaker should be put into add 1.8L deionized water use Ultrasonic Cleaning, ultrasonic frequency is 20Hz, takes out sample after Ultrasonic Cleaning 20min, uses nitrogen to dry up.
Accompanying drawing 1 prepares the preparation of large area cadmium sulphide membrane for use chemical bath method height ammonia condition based on Copper Indium Gallium Selenide substrate under.
Embodiment 2:
Prepare the preparation of large area cadmium sulphide membrane under using chemical bath method height ammonia condition based on Copper Indium Gallium Selenide substrate, its preparation process is as follows:
The preparation of Copper Indium Gallium Selenide substrate: first will obtain CIGS absorbed layer prepared on a glass substrate.
1) cleaning of soda lemon glass
1. the soda glass of 10cm × 10cm is put in heavy hydrogen potassium oxide solution (by 300 grams of potassium hydroxide, the solution of 3 liters of deionized water configurations) and soak 2h; 2. be placed in rinsing clean soda glass the acetone soln that concentration is 99.5%, putting into supersonic wave cleaning machine, to clean ultrasonic frequency be 50kHz, and the time is 30min, can suitably be heated to be 40 DEG C; 3. soda glass is taken out from acetone soln, with deionized water rinsing; 4. then the soda lemon glass substrate alcohol washes washed is dried up with nitrogen.
2) preparation of molybdenum back contact
In the settling chamber of Deposited By Dc Magnetron Sputtering system, take purity as the Mo of 99.99% be target, adopt rf magnetron sputtering preparation system to deposit the molybdenum film of one deck high resistant and low-resistance respectively at substrate surface.1. base vacuum: 3.0 × 10
-4pa, operating air pressure is 1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 600W, Ar throughput is 40sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 2 times.2. operating air pressure is 0.1Pa, and underlayer temperature is room temperature 25 DEG C, and radio-frequency power is 1500W, Ar throughput is 15sccm, and the base target speed of travel is 4mm/s, and sedimentation time (reciprocal time of base target) is 6 times.
3) preparation of CuInGaSe absorbed layer film
1. base vacuum is 4.0 × 10
-4pa, underlayer temperature is 500 DEG C, coevaporation In, Ga, Se initialization layer 2min, and wherein In source temperature is 800 DEG C, and Ga source temperature is 840 DEG C, and Se source temperature is 400 DEG C, and evaporation time is 20min; 2. underlayer temperature is 550 DEG C, coevaporation Cu, Se, and wherein Cu source temperature is 1200 DEG C, and Se source temperature is 250 DEG C, and evaporation time is 20min; What 3. underlayer temperature kept in second step is temperature-resistant, coevaporation In, Ga, Se, and wherein In source temperature is 850 DEG C, and Ga source temperature is 880 DEG C, and Se source temperature is 450 DEG C, and evaporation time is 5min; 4. substrate is cooled, when evaporate substrate to be cooled to while Se 400 DEG C time, close Se evaporation source, then substrate cool to room temperature can be obtained the CIGS thin-film in glass substrate.
4) preparation of cadmium sulfide buffer layer thin film
(1) dosing, use cadmium acetate is cadmium salt, and ammonium acetate is buffer, and thiocarbamide is sulphur source, wiring solution-forming: in order to be made into 0.05M, to get amount of medicament be 26.652g, SC (NH to (CH3COO) 2Cd
2)
2to get it filled product 23.124g for being made into 0.5M, the deionized water and stirring adding 2L is even.By (CH3COO) of 2L
2cd solution mark becomes No. 1 liquid, by SC (NH
2)
22L solution mark become No. 2 liquid.
(2) get reagent and regulate ratio of reagents: No. 1 liquid uses 20mL at every turn, it is the ammoniacal liquor 40mL of 25%-28% that No. 2 liquid is got containing NH3 quality proportion with 25-30mL at every turn, put into the beaker of a 2L, add deionized water be diluted to 1L stir 5min then put into 2L beaker.
(3) sample is placed: size CIGS sample substrate being tailored into 10cm × 10cm, clamp with sawtooth frame in the middle of the beaker put into and be furnished with solvent, samples vertical is put vertical (as shown in Figure 1).
(4) reactive deposition growth: put into water-bath by what be equipped with sample and solvent from beaker, water-bath will be warmed up to 75 DEG C in advance.Initial reaction stage phase solution is transparent, uses magnetic rotor in early stage, and rotor speed control is at 145 revs/min (r/min), and after wait 20min, solution colour becomes muddy, and now stopping rotor should timing 25min.
(5) sample takes out and cleaning: take out sample after becoming muddy rear timing to 25min, and with deionized water rinsing, but due to prepared cadmium sulfide be comprise same qualitative response and heterogeneous response competition reaction prepared by film, because surface has a small amount of precipitation to affect film quality, so 2L beaker should be put into add 1.8L deionized water use Ultrasonic Cleaning, ultrasonic frequency is 25Hz, takes out sample after Ultrasonic Cleaning 25min, uses nitrogen to dry up.
Accompanying drawing 1 is for preparing SEM figure based on preparing large area cadmium sulphide membrane under Copper Indium Gallium Selenide substrate use chemical bath method height ammonia condition.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. under using chemical bath method height ammonia condition based on Copper Indium Gallium Selenide substrate, prepare the preparation of large area cadmium sulphide membrane.It is characterized in that: substrate is made up of MO and CIGS compound substrate prepared by glass substrate, use water-bath to be the bigbore water-bath improving temperature gradient with magnetic rotor.Use and prepare without the chemical bath method that the ammonia concn of buffer is higher the CdS film that area is 10cm × 10cm.
2. prepare large area cadmium sulfide under a use chemical bath method height ammonia condition as claimed in claim 1
Method for manufacturing thin film, is characterized in that:
1) to cleaning and the process of the substrate surface of SLG/Mo/CIGS structure;
2) then the substrate handled well is put into solution by the reagent solution of configuration required for chemical bath; The size of substrate is tailored as 12cm × 12cm;
3) the water-bath temperature constant 80 DEG C will heated in advance, puts into water-bath by the beaker containing substrate and solute and regulates temperature to make sufficient reacting, and produces without precipitation.Rotor is set as 140 revs/min;
4) take out sample after reacting 40min and put into 1L deionized water ultrasonic cleaning 10min.Supersonic frequency controls at 25Hz;
5) sample four edges sanctions respectively being gone 1cm to make 10cm × 10cm avoids edge due to the different lining substrate adsorbs caused of this function of Jebb.
3. setting rotor speed according to claim 2 regulates temperature that sufficient reacting be is characterized in that: under front 20min uses rotor speed to be 140 revs/min and temperature is 80 DEG C of conditions, course of reaction changes to from incipient the crocus becoming muddiness without color, then turns off rotor reaction 30min.Reach the thickness thin film being about 50nm.
4. prepare large area cadmium sulphide membrane preparation method under using chemical bath method height ammonia condition based on Copper Indium Gallium Selenide substrate according to claim 2, it is characterized in that: experimental chemistry metering is than (CH3COO)
2cd: SC (NH2)
2: NH
3=0.001M: 0.0015M: 0.05M, temperature is set as 80 DEG C, (CH3COO)
2in order to be made into 0.05M, to get amount of medicament be 26.652g, SC (NH2) to Cd
2to get it filled product 23.124g for being made into 0.5M, the deionized water and stirring adding 2L is even.By (CH3COO) of 2L
2cd solution mark becomes No. 1 liquid, by CH
3cOONH
42L solution mark becomes No. 2 liquid.Get reagent and regulate ratio of reagents: No. 1 liquid uses 20-25mL, and it is the beaker of 2L that No. 2 liquid put into a volume with 25-30mL at every turn at every turn, getting containing NH3 quality proportion is the ammoniacal liquor 37.5mL of 25%-28%, adds deionized water and is diluted to 1.8L.
5. the use as claim 2 support is with the fixing zig zag stent of use two below, sample is placed on support and vertically places, stirring rotator is in beaker center, and the substrate surface of SLG/Mo/CIGS structure places towards rotor place to make plated film evenly and provide more to adsorb room.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019174609A1 (en) * | 2018-03-14 | 2019-09-19 | 北京铂阳顶荣光伏科技有限公司 | Composite material, chemical bath deposition method and preparation method for cigs photovoltaic module |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019174609A1 (en) * | 2018-03-14 | 2019-09-19 | 北京铂阳顶荣光伏科技有限公司 | Composite material, chemical bath deposition method and preparation method for cigs photovoltaic module |
| JP2019161207A (en) * | 2018-03-14 | 2019-09-19 | 北京▲伯▼陽頂栄光伏科技有限公司 | Composite material, chemical bath deposition method, and preparation method for cigs photovoltaic module |
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