CN102637777A - Chemical preparation technology for solar cell light absorption layer Cu2O nano film - Google Patents

Chemical preparation technology for solar cell light absorption layer Cu2O nano film Download PDF

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Publication number
CN102637777A
CN102637777A CN2012101361474A CN201210136147A CN102637777A CN 102637777 A CN102637777 A CN 102637777A CN 2012101361474 A CN2012101361474 A CN 2012101361474A CN 201210136147 A CN201210136147 A CN 201210136147A CN 102637777 A CN102637777 A CN 102637777A
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cuprous oxide
cu2o
preparation technology
film
solar cell
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杨培志
自兴发
杨雯
彭柳军
邓双
化麒麟
冷天玖
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Yunnan Normal University
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Yunnan Normal University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention provides a chemical preparation technology for a solar cell light absorption layer Cu2O nano film, which belonging to the technical field of the photovoltaic cell. The nanoscale Cu2O is prepared by the electrochemical deposition preparation technology, the average diffusion time of the photon-generated carrier of the nanoscale Cu2O is shortened to be 1/102-1/106, and the compound probability is greatly reduced so as to improve the use ratio of the sunlight. The technical means of the chemical preparation technology comprises specific steps of: A) preparing a precursor by an RF (radio frequency) magnetron sputtering deposition zinc oxide (ZnO) layer; B) carrying out electrochemical deposition on a cuprous oxide (Cu2O) film; and C) annealing a cuprous oxide (Cu2O) film sample.

Description

A kind of solar cell light absorption layer Cu 2The chemical preparating process of O nano thin-film
Technical field:
The present invention relates to a kind of preparation technology of solar cell light absorption layer thin-film material, belong to the photovoltaic cell technical field.
Background technology:
Cuprous oxide (Cu 2O) be one of found semi-conducting material the earliest, because advantage such as it is nontoxic, preparation cost is low, material extensively is easy to get has received numerous researchers' attention.Cu 2O is the direct gap semiconductor material with cubic structure, and its energy gap is about 2.17eV, can is the excited by visible light of 800 ~ 400nm by wavelength.The Cu of polycrystalline attitude 2O can recycle and can not be reduced to Cu (O) or be oxidized to Cu (II), and is promptly stable fine, so Cu 2O is the very big semi-conducting material of a kind of application potential, and it is widely used in various fields, as, solar cell, efficiency light chemical cell optoelectronic pole, magnetic device and photocatalysis etc.Especially on solar cell, can be according to the different resistivity of preparation condition 10 3～10 13Change in the Ω .cm scope, the absorption coefficient of visible-range is higher, and its theoretical conversion efficient can reach 20%, and this makes it become possibility as the absorbed layer of film heterojunction battery, but its photoelectric conversion efficiency is lower up to now.
Cu 2O is a kind of typical P type semiconductor material, at present, realizes that its n type doping is also very difficult, thereby also is difficult to prepare Cu 2O homojunction battery, but Cu 2O can form the Cu with Schottky potential barrier or heterojunction with other material 2O solar cell, for example Cu 2The Schottky barrier cell of O/Cu, Cu 2O/ZnO and Cu 2The heterojunction battery of O/CdS.Cu 2The preparation method of O thin-film material is known to have vacuum thermal evaporation, chemical oxidation, thermal oxidation, sputter, chemical vapour deposition (CVD) and electrochemical deposition etc.Cu 2The preparation of O thin-film material still is faced with many problems and difficulty, Cu 2The influence of O film phase constituent and pattern also is not very clear, the Cu that makes 2The O particle diameter is big (micron order).Micron order Cu 2The diffusion length of photo-generated carrier is oversize among the O, and it is just compound often to have little time the surface, so photoelectric conversion efficiency is lower.If but particle diameter is reduced to nanoscale from micron order, the average diffusion time of photo-generated carrier will be reduced to 1/10 2~ 1/10 6, recombination probability also can reduce greatly, thereby causes the raising of sunlight utilance.Therefore, nanometer Cu 2The preparation of O film is a key factor for improving the solar energy utilization ratio.Patent (application number: 200310112821) adopt the metallic copper anodes cuprous oxide that electrolysis generates in the electrolyte that contains acetonitrile and oxolane, calcine 400～600 ℃ of nitrogen protections by the cuprous oxide that makes.Electrolyte contains poisonous composition in the method technology, needs high-temperature process simultaneously, in the solar cell preparation, has unfavorable conditions.
Summary of the invention:
For solving the problem that background technology proposes, the object of the present invention is to provide a kind of solar cell light absorption layer Cu 2The chemical preparating process of O nano thin-film is prepared nanoscale Cu through process for electrochemical deposition preparation 2O makes the average diffusion time of its photo-generated carrier will be reduced to 1/10 2~ 1/10 6, recombination probability reduces greatly, thereby improves the utilance of sunlight.
For realizing above-mentioned purpose, the present invention adopts following technological means: concrete steps comprise:
A, RF rf magnetron sputtering depositing zinc oxide (ZnO) layer preparation presoma: the substrate of tin indium oxide (ITO) electro-conductive glass is cleaned with washing agent earlier; Adopt the acetone ultrasonic cleaning again; After spend dried up the cleaning, in the clean drying box of sealing, dry at last; Prepare presoma with the RF rf magnetron sputtering at substrate sputtering zinc oxide (ZnO) layer;
B, electrochemical deposition cuprous oxide (Cu 2O) film: the mixed liquor of preparation copper sulphate (CuSO4), sodium lactate (CH3CH (OH) COONa); Add NaOH (NaOH) at mixed liquor, the pH value of solution is adjusted into 12; Adopt the three-electrode electro Chemical system, promptly a platinum is used to deposit cuprous oxide (Cu2O) film to electrode and Ag|AgCl reference electrode, preparation cuprous oxide (Cu2O) film sample;
C, cuprous oxide (Cu 2O) film sample annealing in process: deposited samples is placed in the quartzy stove, in quartzy stove, charge into nitrogen, by the certain speed gradient sample is heated to constant temperature, and keeps a period of time, take out sample at last and naturally cool to room temperature.
Copper sulphate among the said step B in the used mixed liquor of electrochemical deposition: the mol ratio=1:12.5 of sodium lactate;
Cuprous oxide (Cu among the said step C 2O) nitrogen flow that charges into of film sample annealing in process is 0.1m3/h; Said temperature gradient is 60 ℃ of min -1, be heated to 180 ℃, and keep 30min.
The present invention compares the advantage that has and positive beneficial effect with known technology:
A. electrochemical deposition of the present invention adopts the constant potential mode, need not to stir, and deposition can be controlled through monitoring deposited charge amount, and is simple to operate, and can the large tracts of land deposition;
B. the present invention is through control solution temperature and substrate, can realize the controllable growth of membrane structure and thickness, cost is low, purity is high, measuring, cuprous oxide (Cu 2O) film has nanocrystalline structure, and crystallite dimension is 80-150nm.
Description of drawings:
Fig. 1 is cuprous oxide (Cu provided by the invention 2O) thin film preparation process flow chart.
Fig. 2 is cuprous oxide (Cu provided by the invention 2O) thin film electrochemistry precipitation equipment sketch map.1 is work electrode among the figure; 2 is zinc oxide (ZnO) layer presoma; 3 is electrolyte; 4 is the electrochemical deposition case; 5 is the Ag|AgCl reference electrode; 6 is electrochemical workstation; 7 are electrode connection lead; 8 is that platinum is to electrode
Fig. 3 is cuprous oxide (Cu provided by the invention 2O) thin film deposition structural representation.
Embodiment:
Embodiment 1
(1) with tin indium oxide (ITO) electro-conductive glass (substrate of 30mm * 50mm * 1mm) is cleaned with washing agent earlier, adopts the acetone ultrasonic cleaning again 15 minutes, after spend dried up the cleaning, in the clean drying box of sealing, dry at last;
(2) in substrate, adopt thick zinc oxide (ZnO) layer (presoma) of RF rf magnetron sputtering deposition 1-2 μ m;
(3) spend dried up preparing electrolyte: electrolyte is for containing 0.4 mol sulfuric acid copper (CuSO 4), 5 molar lactic acid sodium (CH 3CH (OH) COONa) mixed liquor; Add NaOH (NaOH) at mixed liquor, the pH value of solution is adjusted into 12;
(4) adopt three-electrode electro Chemical system (work electrode, to electrode and reference electrode); With the zinc oxide (ZnO) for preparing layer (presoma) as work electrode, adopt the platinum sheet as to electrode, employing Ag|AgCl as reference electrode, in the electrolyte for preparing, deposit cuprous oxide (Cu 2O) thin layer.Deposition process adopts constant potential (Autolab 20 pressurizers) mode, Cu 2The chemical potential of O deposition is-0.4 V (volt) (with respect to the .Ag|AgCl reference electrode), under 70 ℃ depositing temperature, does not have to stir and carries out, and deposition is controlled about 60 min of sedimentation time through monitoring deposited charge amount;
(5) with the cuprous oxide (Cu of deionized water clean deposition 2O) film sample dries naturally;
(6) cuprous oxide (Cu 2O) film sample annealing in process: deposited samples is placed in the quartzy stove, in quartzy stove, charge into nitrogen (flow 0.1m 3/ h), with 60 oC.min -1The velocity gradient of (per minute 60 degree) is heated to 180 with sample oC, and keep 180 oC furnace temperature 30 min;
(7) take out sample and naturally cool to room temperature, obtain the thick cuprous oxide (Cu of 2-3 μ m 2O) film.

Claims (3)

1. solar cell light absorption layer Cu 2The chemical preparating process of O nano thin-film is characterized in that, may further comprise the steps:
A, RF rf magnetron sputtering depositing zinc oxide layer prepare presoma: the indium tin oxide-coated glass substrate is cleaned with washing agent earlier, adopts the acetone ultrasonic cleaning again, after spend dried up the cleaning, in the clean drying box of sealing, dry at last; Prepare presoma with the RF rf magnetron sputtering at substrate sputtering zinc oxide layer;
B, electrochemical deposition cuprous oxide film: the mixed liquor of preparation copper sulphate, sodium lactate; Add NaOH at mixed liquor, the pH value of solution is adjusted into 12; Adopt the three-electrode electro Chemical system, promptly a platinum is used to deposit cuprous oxide film to electrode and Ag|AgCl reference electrode, preparation cuprous oxide film sample;
C, cuprous oxide film sample annealing in process: deposited samples is placed in the quartzy stove, in quartzy stove, charge into nitrogen, by the certain speed gradient sample is heated to constant temperature, and keeps a period of time, take out sample at last and naturally cool to room temperature.
2. preparation technology according to claim 1 is characterized in that: the copper sulphate among the said step B in the used mixed liquor of electrochemical deposition: the mol ratio=1:12.5 of sodium lactate.
3. preparation technology according to claim 1 and 2 is characterized in that: cuprous oxide (Cu among the said step C 2O) nitrogen flow that charges into of film sample annealing in process is 0.1m 3/ h; Said temperature gradient is 60 ℃ of min -1, be heated to 180 ℃, and keep 30min.
CN2012101361474A 2012-05-04 2012-05-04 Chemical preparation technology for solar cell light absorption layer Cu2O nano film Pending CN102637777A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103882494A (en) * 2014-03-12 2014-06-25 浙江大学 Preparation method of Cu2O/ZnO heterojunction material
CN103924277A (en) * 2014-04-23 2014-07-16 桂林理工大学 Preparation method of spherical CdSe/Cu2O heterojunction material
CN105185859A (en) * 2015-06-15 2015-12-23 华南师范大学 Manufacturing method for efficient heterojunction inorganic solar energy cells
CN108323212A (en) * 2016-02-18 2018-07-24 田永权 Solar cell and preparation method thereof
CN108560012A (en) * 2018-05-12 2018-09-21 辽宁大学 High-photoelectric transformation efficiency Sn2Nb2O7Light anode and its preparation method and application
CN108767103A (en) * 2018-05-29 2018-11-06 桂林电子科技大学 A kind of high-performance p-type α-MgAgSb base thermoelectricity materials and preparation method thereof
CN111610240A (en) * 2020-06-04 2020-09-01 南京邮电大学 Photoelectric biosensor constructed based on cathode photoelectrode

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US20100038638A1 (en) * 2008-08-13 2010-02-18 Board Of Regents, The University Of Texas System N-type Doping in Metal Oxides and Metal Chalcogenides by Electrochemical Methods
CN102214734A (en) * 2011-06-07 2011-10-12 济南大学 Method for manufacturing zinc oxide/cuprous oxide thin film solar cell
CN102321901A (en) * 2011-09-21 2012-01-18 浙江理工大学 Heat treatment method for increasing n-type cuprous oxide film carrier concentration

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US6258702B1 (en) * 1997-11-12 2001-07-10 Canon Kabushiki Kaisha Method for the formation of a cuprous oxide film and process for the production of a semiconductor device using said method
US20100038638A1 (en) * 2008-08-13 2010-02-18 Board Of Regents, The University Of Texas System N-type Doping in Metal Oxides and Metal Chalcogenides by Electrochemical Methods
CN102214734A (en) * 2011-06-07 2011-10-12 济南大学 Method for manufacturing zinc oxide/cuprous oxide thin film solar cell
CN102321901A (en) * 2011-09-21 2012-01-18 浙江理工大学 Heat treatment method for increasing n-type cuprous oxide film carrier concentration

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刘英麟 等: "用电化学沉积制备ZnO/Cu2O异质p-n结", 《发光学报》, vol. 25, no. 5, 31 October 2004 (2004-10-31), pages 533 - 536 *
胡飞等: "P型Cu2O半导体薄膜的电化学沉积研究", 《人工晶体学报》, vol. 38, no. 4, 31 August 2009 (2009-08-31), pages 952 - 956 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103882494A (en) * 2014-03-12 2014-06-25 浙江大学 Preparation method of Cu2O/ZnO heterojunction material
CN103924277A (en) * 2014-04-23 2014-07-16 桂林理工大学 Preparation method of spherical CdSe/Cu2O heterojunction material
CN105185859A (en) * 2015-06-15 2015-12-23 华南师范大学 Manufacturing method for efficient heterojunction inorganic solar energy cells
CN105185859B (en) * 2015-06-15 2018-06-26 华南师范大学 The preparation method of High-efficiency heterojunction inorganic solar cell
CN108323212A (en) * 2016-02-18 2018-07-24 田永权 Solar cell and preparation method thereof
CN108560012A (en) * 2018-05-12 2018-09-21 辽宁大学 High-photoelectric transformation efficiency Sn2Nb2O7Light anode and its preparation method and application
CN108560012B (en) * 2018-05-12 2020-02-07 辽宁大学 High photoelectric conversion efficiency Sn2Nb2O7Photo-anode and preparation method and application thereof
CN108767103A (en) * 2018-05-29 2018-11-06 桂林电子科技大学 A kind of high-performance p-type α-MgAgSb base thermoelectricity materials and preparation method thereof
CN111610240A (en) * 2020-06-04 2020-09-01 南京邮电大学 Photoelectric biosensor constructed based on cathode photoelectrode
CN111610240B (en) * 2020-06-04 2022-11-15 南京邮电大学 Photoelectric biosensor constructed based on cathode photoelectrode

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Application publication date: 20120815