CN103094422A - Doping craft in copper-zinc oxide tin sulphur selenium film preparation - Google Patents

Doping craft in copper-zinc oxide tin sulphur selenium film preparation Download PDF

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CN103094422A
CN103094422A CN2013100335867A CN201310033586A CN103094422A CN 103094422 A CN103094422 A CN 103094422A CN 2013100335867 A CN2013100335867 A CN 2013100335867A CN 201310033586 A CN201310033586 A CN 201310033586A CN 103094422 A CN103094422 A CN 103094422A
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doping
film
zinc tin
copper zinc
tin sulfur
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向勇
张晓琨
张庶
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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Abstract

The invention provides a doping craft in copper-zinc oxide tin sulphur selenium film preparation, and belongs to the technical field of a solar cell. According to the doping craft, a fifth main group element can be effectively doped, doping gradient is controllable, doping proportion is adjustable, and doping effect is obvious. The doping craft comprises a first of preparing a copper-zinc oxide tin sulphur selenium film by applying of thin film deposition craft, a second step of doping the fifth main group element into the copper-zinc oxide tin sulphur selenium film through the doping craft according to selected craft and needed doping elements in the process of preparing of the copper-zinc oxide tin sulphur selenium film, and a third step of carrying out technology for heating process to the film, and therefore activation of doping effect of the fifth main group element in the copper-zinc oxide tin sulphur selenium film is finished at last. The purposes that crystallization properties, current-illumination characteristics, electrical properties of the copper-zinc oxide tin sulphur selenium film are improved and optimized are achieved, and the doping craft has wide application prospect in the film solar cell with low cost and high efficiency.

Description

Doping process in the copper zinc tin sulfur selenium film preparation
Technical field
The present invention relates to technical field of solar batteries, specifically refer to the doping process in a kind of copper zinc tin sulfur selenium film preparation.
Background technology
The quaternary compound copper zinc tin sulfur selenium of custerite structure is direct gap semiconductor, and the desired best energy gap of its energy gap and solar cell (1.5 eV) is very approaching, absorption coefficient large (10 4cm -1Magnitude), component element amount of containing on the earth's crust is abundant, the exploitation difficulty is low, huge to environment nonhazardous pollution, annual production.Solar cell based on copper zinc tin sulfur selenium might become in future the main flow photovoltaic technology.
Through the prior art literature search is found, in the Copper Indium Gallium Selenide class material similar to copper zinc tin sulfur selenium, the application that improves the absorbed layer film by element doping has more and more caused the concern of industry, for example the sodium sputtering doping method of the disclosed a kind of extensive CIGS base film photovoltaic material of CN102347398A.Min Yuan etc. are at the 852nd to 856 page of " Antimony assisted low-temperature processing of CuIn that delivers of " Thin Solid Film " the 519th volume (second phase) in 2010 1-xGa xSe 2-yS ySolar cells " in, the performance that can significantly promote prepared copper indium gallium selenium solar cell by the doping of the 5th major element antimony reported.
Different doping processs, the effect in different copper zinc tin sulfur selenium thin film preparation processes is different, therefore, comprehensively explores various possible doping processs, and doping process is applied to technical field of solar batteries, and is significant for this area.
Summary of the invention
The objective of the invention is to propose the doping process in a kind of copper zinc tin sulfur selenium film preparation, be specially the technique of the 5th major element that effectively adulterates in the copper zinc tin sulfur selenium film, this kind doping process doping gradient is controlled, doping ratio is adjustable, doping effect is remarkable.
For achieving the above object, the technical solution used in the present invention comprises following steps:
Step 1: by the applied film depositing operation, preparation copper zinc tin sulfur selenium film; Described thin film deposition processes comprises element evaporation process, compound evaporation process, element reaction sputter sulfuration process, compound sputter sulfuration process, nano particle technique and electroplating technology etc.
Step 2: the technique of selecting during according to preparation copper zinc tin sulfur selenium film and the characteristics that need doped chemical, realize the doping of this element in the copper zinc tin sulfur selenium film by doping process; Described doping process comprises chemical bath depositing operation, electroplating deposition thin-film technique, ion implantation technology and reactant and raw material doping process etc.
Step 3: the gained film is imposed Technology for Heating Processing, finally complete the activation of the 5th major element doping effect in the copper zinc tin sulfur selenium film.
Technical scheme of the present invention is in implementation process, and in order to obtain the film of special dopant profiles gradient, in step 2, the preparation of doping sedimentary deposit can be implemented before the copper zinc tin sulfur selenium thin film deposition.
The present invention has following outstanding beneficial effect: the doping process in the copper zinc tin sulfur selenium film preparation that the present invention proposes, be very beneficial for promoting the doping effect of various the 5th major elements in the copper zinc tin sulfur selenium film of different depositing operation preparations, and realized that tool has a broad prospect of the use in the preparation of low-cost high-efficiency thin-film solar cells to the improving and optimizating of copper zinc tin sulfur selenium thin film crystallization performance, photoelectric characteristic, electrology characteristic.
Description of drawings
Below in conjunction with accompanying drawing, the invention will be further described.
Fig. 1 is the flow chart of doping process of the present invention.
Fig. 2 is that the preferred application case effect of doping process of the present invention in the copper zinc tin sulfur selenium film preparation showed.
Embodiment
Technical scheme flow chart of the present invention as shown in Figure 1, and is concrete, can be divided into three key steps of introducing, heat treatment of copper zinc tin sulfur selenium thin film technology, doped chemical.
According to the difference of above-mentioned three key step enforcements order, now divide three types to introduce specific embodiments.
Type one: at first pass through thin film deposition processes, optional technique comprises that the means such as element evaporation process, compound evaporation process, element reaction sputter sulfuration process, compound sputter sulfuration process, nano particle technique or electroplating technology prepare the copper zinc tin sulfur selenium film, complete doping to the 5th major element by chemical bath depositing operation, electroplating deposition thin-film technique or ion implantation technology afterwards, by heat treatment, complete whole technical process again.
Type two: the deposition of at first completing the doped layer film by chemical bath depositing operation or electroplating deposition thin-film technique, complete the copper zinc tin sulfur selenium thin film technology by the technique of preparation copper zinc tin sulfur selenium film afterwards, optional technique comprises element evaporation process, compound evaporation process, element reaction sputter sulfuration process, compound sputter sulfuration process, nano particle technique or electroplating technology etc., by heat treatment, complete whole technical process again.
Type three: when preparing the copper zinc tin sulfur selenium film by optional techniques such as element evaporation process, compound evaporation process, element reaction sputter sulfuration process, compound sputter sulfuration process, nano particle technique or electroplating technologies, by ground and mixed, use the doping target, add the mode such as doped chemical forerunner in the wet chemical system, mix the object element of the 5th main group in its source material, can realize like this doping of the 5th major element in the copper zinc tin sulfur selenium film of preparation.
The below describes respectively chemical bath depositing operation, electroplating deposition thin-film technique, ion implantation technology and reactant and four kinds of doping processs of raw material doping process in detail.
The technical process of chemical bath depositing operation doping the 5th major element is as follows: compound concentration is the sodium thiosulfate solution of 1.15 mol/L, be labeled as A liquid, compound concentration is the antimony chloride acetone soln of 5 mol/L, be labeled as B liquid, under 30 ℃ (water-bath temperature control), B liquid slowly dropped in A liquid, and follow soft stirring, after A, the mixing of B liquid are completed, substrate is inserted in mixing material, complete the deposition of doped chemical sulfide film after 2.5 h; This technical process is equally applicable to deposit its sulfide film take bismuth chloride or arsenic chloride as raw material; This process can be carried out before substrate in the copper zinc tin sulfur selenium thin film deposition, also can carry out after the deposition of completing the copper zinc tin sulfur selenium film, with the differentiation regulation and control of distribution gradient in the copper zinc tin sulfur selenium film of realizing doped chemical.
The technical process of electroplating deposition thin-film technique doping the 5th major element is as follows: at first configuration contains the electrolyte of target doped chemical, water is as solvent, and its formula is as follows: tartaric acid (0.1 mol/L), natrium citricum (0.2 mol/L), sodium thiosulfate (Na 2S 2O 3, 0.11 mol/L), antimony chloride or bismuth chloride (SbCl 3Or BiCl 3, 0.6 mol/L); Use afterwards this electrolyte at 1.1 V current potential deposit antimony chloride or bismuth chloride films; This process can be carried out before substrate in the copper zinc tin sulfur selenium thin film deposition, also can carry out after the deposition of having completed the copper zinc tin sulfur selenium film, with the differentiation regulation and control of distribution gradient in the copper zinc tin sulfur selenium film of realizing doped chemical.
The technical process of ion implantation technology doping the 5th major element is as follows: ion implantation technology mainly is applicable to the doping of P elements, arsenic element and antimony element, the ion implantor of using in microelectronics manufacture is realized the doping of above-mentioned element in the copper zinc tin sulfur selenium film that has prepared, and the magazine source of corresponding phosphorus, arsenic, antimony is respectively phosphine (PH 3), arsine (AsH 3), Antimony pentachloride (SbCl 5).
The process of raw material doping process is as follows: in the raw material that various preparation copper zinc tin sulfur selenium thin-film techniques are used, sneak into the target doped chemical, and then realize the doping therein of the 5th major element in the preparation thin-film process, specifically can be described below: 1) in element evaporation process and compound evaporation process, metal simple-substance or the sulfide of the arsenic by sneaking into the target doping ratio in raw material, antimony, bismuth, milled processed mixes it, completes the doping of the 5th major element in the raw material of this class technique; 2) in element reaction sputter sulfuration process, compound sputter sulfuration process, when making target, the arsenic of the target proportion of adulterating therein, antimony, bismuth element are realized the raw material doping in sputtering technology; 3) in nano particle technique, when the nano particle of synthetic copper zinc tin sulfur selenium, sneak into the pre-reaction material of the 5th major element in reaction system, make it participate in synthetic reaction, can realize the doping of the 5th major element in the standby raw material of copper zinc tin sulfur selenium film of nano particle legal system, its doping ratio can be by the proportional control of the 5th major element reaction precursor that adds; When 4) using electroplating technology to prepare the copper zinc tin sulfur selenium film, add the composition that contains the 5th major element in electrolyte, and adjust current potential to suitable numerical value, and can realize the plating codeposition of doped chemical and copper zinc tin sulfur selenium, complete the doping of the 5th major element in electroplating technology.
Fig. 2 is a preferred embodiment of the present invention, in application compound reactive sputtering sulfuration process prepares the process of copper zinc tin sulfur selenium film, after sputter is complete, after being deposited thereon deposition antimony trisulfide film and Technology for Heating Processing by chemical bath, significantly improved the crystal property of copper zinc tin sulfur selenium film, S001 is for using the embodiment effect displaying of doping process of the present invention, and S002 shows for using contrast effect of the present invention.
Although the present invention has been described in detail with reference to selection process scheme, Figure of description and preferred embodiment, to one skilled in the art, various uses of the present invention and distortion can not depart from essence of the present invention and scope and complete.Therefore, at Figure of description and the embodiment of this detailed description, be not that attempt is done any pro forma restriction to the present invention according to this, therefore, all work under identical creation spirit about any modification of the present invention or conversion all must be in the category that the invention is intended to protect.

Claims (9)

1. the doping process in a copper zinc tin sulfur selenium film preparation is characterized in that: comprise the following steps:
Step 1: by the applied film depositing operation, preparation copper zinc tin sulfur selenium film; Described copper zinc tin sulfur selenium thin film preparation process comprises element evaporation process, compound evaporation process, element reaction sputter sulfuration process, compound sputter sulfuration process, nano particle technique, electroplating technology;
Step 2: the technique of selecting during according to preparation copper zinc tin sulfur selenium film and the characteristics that need doped chemical, realize the doping of this element in the copper zinc tin sulfur selenium film by doping process; Described doping process comprises chemical bath depositing operation, electroplating deposition thin-film technique, ion implantation technology, reactant and raw material doping process;
Step 3: the gained film is imposed Technology for Heating Processing, finally complete the activation of the 5th major element doping effect in the copper zinc tin sulfur selenium film.
2. the doping process in a kind of copper zinc tin sulfur selenium film preparation according to claim 1, it is characterized in that: described element evaporation process, compound evaporation process, element reaction sputtering technology and compound reactive sputtering process, use vacuum evaporation equipment, take the solid material of the solid material of copper, zinc, tin, sulphur, selenium element simple substance or its compound as raw material, prepare the technique of copper zinc tin sulfur selenium film by physics vapor phase deposition techniques such as vacuum evaporation, sputter coatings.
3. the doping process in a kind of copper zinc tin sulfur selenium film preparation according to claim 1 is characterized in that: described nano particle technique comprises the preparation of nano particle preparation, the copper zinc tin sulfur selenium nanometer ink of copper zinc tin sulfur selenium, based on technical processs such as the thin film deposition processes film forming of nano ink, annealing heat treatments; Described electroplating technology comprises the lamination metal preformed layer electroplating deposition of copper, zinc, tin, sulfuration or the selenizing heat treatment process of lamination metal preformed layer.
4. the doping process in a kind of copper zinc tin sulfur selenium film preparation according to claim 1, it is characterized in that: described chemical bath dopant deposition technique and electroplating deposition thin-film technique, at copper zinc tin sulfur selenium film upper surface or lower surface, by chemical bath depositing operation or electroplating deposition thin-film technique, deposition comprises the film of the 5th major element, and realizes the doping of the 5th major element in the copper zinc tin sulfur selenium film by heat treatment.
5. the doping process in a kind of copper zinc tin sulfur selenium film preparation according to claim 1, it is characterized in that: described reactant and raw material doping process, mean in preparing the process of copper zinc tin sulfur selenium film by element evaporation process, compound evaporation process, element reaction sputter selenium sulfide metallization processes, compound sputter selenium sulfide metallization processes, nano particle technique, by doping the 5th major element in reactant or raw material, realize the purpose of doping target the 5th major element in deposit film.
6. the doping process in a kind of copper zinc tin sulfur selenium film preparation according to claim 1, it is characterized in that: described the 5th major element ion implantation doping process, select suitable ion source, by ion implantor, foreign ion is injected in the copper zinc tin sulfur selenium film, activate the doping ion by Technology for Heating Processing again, complete doping.
7. the doping process in described a kind of copper zinc tin sulfur selenium film preparation of according to claim 1 to 6, it is characterized in that: the chemical composition of described copper zinc tin sulfur selenium material is Cu aZn bSn c(S xSe 1-x) d, 0≤x≤1 wherein, stoichiometric number a, b, c, d satisfy following relation: 0.5≤a/ (b+c)≤1.5,0.8≤b/c≤1.8,1≤d/a≤2.8.
8. the doping process in a kind of copper zinc tin sulfur selenium film preparation according to claim 7, it is characterized in that: the copper zinc tin sulfur selenium material have wurtzite structure or custerite structure or stannite structure crystal structure, film thickness is less than 2 nanometers and greater than 500 microns.
9. the doping process in a kind of copper zinc tin sulfur selenium film preparation according to claim 1, it is characterized in that: described the 5th major element comprises phosphorus, arsenic, antimony, four kinds of elements of bismuth, the doping source comprises its simple substance and compound, and the component ratio of doped chemical in film is greater than 0.01% and less than 15%.
CN2013100335867A 2013-01-29 2013-01-29 Doping craft in copper-zinc oxide tin sulphur selenium film preparation Pending CN103094422A (en)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN103668361A (en) * 2013-10-18 2014-03-26 国家电网公司 Preparation method of copper-indium-zinc-selenium film of photovoltaic battery for photovoltaic power generation system
CN104617186A (en) * 2015-02-06 2015-05-13 中南大学 Surface treatment method of custerite structure thin film solar cell light absorption layer
CN104795468A (en) * 2015-04-20 2015-07-22 岭南师范学院 Copper-zinc-tin film, copper-zinc-tin-sulphur solar cell and production method of copper-zinc-tin film
CN106784038A (en) * 2017-01-05 2017-05-31 上海应用技术大学 A kind of preparation method of the adjustable optoelectronic film of component
CN109904259A (en) * 2019-04-10 2019-06-18 广东工业大学 A kind of codope copper-zinc-tin-sulfur film and preparation method thereof
WO2021135089A1 (en) * 2019-12-31 2021-07-08 肇庆市华师大光电产业研究院 Cu2znbi2s3 nano-rod and use thereof

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Publication number Priority date Publication date Assignee Title
CN103668361A (en) * 2013-10-18 2014-03-26 国家电网公司 Preparation method of copper-indium-zinc-selenium film of photovoltaic battery for photovoltaic power generation system
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CN104617186A (en) * 2015-02-06 2015-05-13 中南大学 Surface treatment method of custerite structure thin film solar cell light absorption layer
CN104795468A (en) * 2015-04-20 2015-07-22 岭南师范学院 Copper-zinc-tin film, copper-zinc-tin-sulphur solar cell and production method of copper-zinc-tin film
CN106784038A (en) * 2017-01-05 2017-05-31 上海应用技术大学 A kind of preparation method of the adjustable optoelectronic film of component
CN106784038B (en) * 2017-01-05 2018-03-13 上海应用技术大学 A kind of preparation method of the adjustable optoelectronic film of component
CN109904259A (en) * 2019-04-10 2019-06-18 广东工业大学 A kind of codope copper-zinc-tin-sulfur film and preparation method thereof
WO2021135089A1 (en) * 2019-12-31 2021-07-08 肇庆市华师大光电产业研究院 Cu2znbi2s3 nano-rod and use thereof

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