WO2015016650A1 - 태양전지 광흡수층 제조용 3층코어-쉘 나노 입자 및 이의 제조 방법 - Google Patents

태양전지 광흡수층 제조용 3층코어-쉘 나노 입자 및 이의 제조 방법 Download PDF

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WO2015016650A1
WO2015016650A1 PCT/KR2014/007091 KR2014007091W WO2015016650A1 WO 2015016650 A1 WO2015016650 A1 WO 2015016650A1 KR 2014007091 W KR2014007091 W KR 2014007091W WO 2015016650 A1 WO2015016650 A1 WO 2015016650A1
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Prior art keywords
shell
core
nanoparticles
layer core
solution
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PCT/KR2014/007091
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English (en)
French (fr)
Inventor
이호섭
윤석희
윤석현
박은주
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주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2016519463A priority Critical patent/JP6316947B2/ja
Priority to CN201480034054.8A priority patent/CN105308758B/zh
Priority to US14/898,473 priority patent/US9478684B2/en
Priority to EP14832179.7A priority patent/EP2996159B1/en
Priority to ES14832179T priority patent/ES2708374T3/es
Publication of WO2015016650A1 publication Critical patent/WO2015016650A1/ko

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    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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    • H01L31/0264—Inorganic materials
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    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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Definitions

  • the present invention relates to a three-layer core-shell nanoparticles for producing a solar cell light absorption layer and the preparation thereof.
  • CZTS Cu 2 ZnSn (S, Se) 4
  • the CZTS has a direct band gap of about 1.0 to 1.5 eV. band gap
  • absorption coefficients of more than 10 4 cm- 'and have the advantage of using relatively rich reserves and low cost Sn and Zn.
  • WO2007-134843 is a vacuum method for sputtering.
  • a method of forming a CZTS layer by simultaneously or sequentially stacking Zn and Sn, followed by heat treatment under an S or Se atmosphere is described in some papers (Phys, Stat. Sol. C. 2006, 3, 2844./Prog. Photovolt: Res. Appl. 2011; 19: 93-96) discloses a method for forming a CZTS layer by simultaneously depositing Cu, Zn, Sn, S, or Se on a substrate by vacuum simultaneous evaporation. , The above techniques are relatively well controlled The advantage is that it is possible to deposit in a state, but the use of expensive equipment has a high process cost, which limits production.
  • PCT / US / 2010-035792 discloses a method of forming a thin film by heat treatment on a substrate using an ink containing CZTS / Se precursor particles, and related to the method of forming the CZTS precursor particles. Journal JACS, 2009, 131,
  • US2011-0097496 Discloses a method of forming a CZTS layer through heat treatment and selenization in a subsequent process by using Cu, Zn and Sn salts dissolved in excess of S or Se in hydrazine as a precursor for forming a CZTS layer.
  • high-temperature injection is problematic for safety, and the solution process using hydrazine is highly toxic and highly explosive, because it is a highly explosive solvent with a hydrazine containing an excess of S or Se. There is a risk inherent and the process is difficult to handle because it is not available to handle.
  • the present invention aims to solve the above-mentioned problems of the prior art and technical problems that have been requested from the past.
  • the inventors of the present application included a core containing copper (Cu) -containing chalcogenide, and (i) a tin (Sn) -containing chalcogenide.
  • a second shell comprising a first shell and a zinc (Zn) -containing chalcogenide; Or (ii) a first shell comprising zinc (Zn) -containing chalcogenide and a second shell comprising tin (Sn) -containing chalcogenide; a three-layer core-shell structured nano
  • the light absorbing layer by using particles, it is possible to increase the productivity by inexpensive and safe process, and to provide a thin film that is uniform in composition and stable to oxidation, and has a high density light absorbing layer for CZTS solar cells. It was confirmed that the growth of the photoelectric efficiency can be improved, and the present invention was completed.
  • the three-layer core-shell structured nanoparticles are used in solar cells.
  • 3-layer core-shell structured nanoparticles forming a light absorption layer comprising: a core containing copper (Cu) -containing chalcogenide;
  • 'core' is mainly used in nanoparticles of various kinds.
  • the material located in the core part means the first synthesized particles
  • the 'shell' refers to the whole surface of the core or other kinds of particles synthesized with the core particles at the surface of the particles divided into cores.
  • the shell encompasses not only the entire surface of the core, but also at least some of the core. Particles in this composite core-shell structure can be seen in hundreds of nanometers. Two different types of shells, cored by cores, coexist and are advantageous in controlling the composition ratio of the trivalent support station required to form the light absorption layer.
  • the chalcogenide is a group VI element, for example sulfur (S) and / or
  • Se selenium
  • the copper (Cu) -containing chalcogenide consists of CuS, Cu x S (1.7 ⁇ x ⁇ 2.0), CuSe, and Cu y Se (1.7 ⁇ y ⁇ 2.0). It may be one or more selected from, and may be at least one selected from the group consisting of Cu 2 S, CuS, Cu 2 Se, and CuSe, more specifically CuS and / or CuSe.
  • the tin (Sn) -containing chalcogenide may be SnS, and / or SnSe
  • the zinc (Zn) -containing chalcogenide may be ZnS, and / or ZnSe.
  • the nanoparticles used in the thin film should be in the form of Cu, Zn, Sn, but not CZTS crystals.
  • Metal nanoparticles composed of a single metal element are easy to oxidize, and are subsequently subjected to excess Se and high temperature. There is a disadvantage in that an oxygen removal process is required.
  • oxidation of the chalcogenide element is appropriately supplied in a high temperature process to form a CZTS thin film. It revealed that it can be prevented.
  • the uniformity of composition can be secured as compared with the case of using several kinds of nanoparticles containing respective elements.
  • the composition ratio of the final CZTS thin film because it is easy to control the ratio of Cu, Zn, Sn in the particle by controlling the ratio of the material constituting the core and the shell, and to form the CZTS thin film of various composition ratios. It is also possible to use.
  • nanoparticles of three-layer core-shell structure having a sequence other than the structure according to the present invention are difficult to manufacture, but have special advantages.
  • a Cu salt is used to produce a copper (Cu) -containing chalcogenide shell in the core particles of a zinc (Zn) -containing chalcogenide
  • the core-shell is due to the difference in the silver tendency of Zn and Cu.
  • the Zn part of the zinc (Zn) -containing chalcogenide core is easily ionized to reduce Cu, and therefore the zinc (Zn) -containing chalcogenide core and copper (Cu) -containing chalcogenide shell are formed. It is easy to form a mixed form in which Cu, Zn, and the like are not uniformly distributed, and there is a problem in that an ionized portion of Zn is combined with oxygen to form an oxide.
  • the core may have a particle diameter of 20 to 200 nanometers. Outside the range, cores containing copper (Cu) -containing chalcogenides may be extended to shells.
  • the size of the core-shell structured nanoparticles is so large that the voids between the particles in the final thin film, having a thickness of 1 micrometer to 2 micrometers, are not desirable, and if the core size is too small, Not only is it easy to aggregate, but it is not desirable to obtain a shell that wraps the surface of the core in order to ensure that the final thin film has an appropriate composition ratio.
  • reaction time, reaction temperature and reaction water reaction when forming the first shell or the second shell on the surface thereof are controlled by zinc knives included in the material constituting the shell formed by controlling the reaction.
  • the weight of cogenide is copper
  • the weight of the first shell and the second shell is preferably determined by considering the overall composition ratio of the target CZTS thin film and the composition ratio with the core.
  • the present invention also provides a method for manufacturing nanoparticles having a three-layer core-shell structure, wherein the manufacturing method includes
  • a mixture is prepared by mixing the first solution and the second solution.
  • step (Iv) mixing the third solution or the fourth solution with the product containing the core particles of step (iii) to form a first shell;
  • the third shell is formed by mixing the fourth solution or the third solution with a product containing the core-shell structured nanoparticles in which the first shell is formed in the process (iv). Synthesizing and refining nanoparticles of structure;
  • the solvents of the first to fourth solutions are different from each other.
  • It may be one or more selected from the group consisting of dimethyl formamide.
  • glycol solvent is not limited, for example,
  • It may be any one selected from the group consisting of ethylene glycol, diethylene glycol, NMP, diethylene glycol monoethyl ether (DEGMEE), and triethylene glycol. .
  • the manufacturing method of the three-layer core-shell structured nanoparticles according to the present invention is achieved by the solution process, so that the process cost can be reduced, and no toxic substances are used to prepare the solution. It is possible to reduce the residue of carbon in the formation of CZTS thin film by reducing the use of the agent.
  • the Group VI source included in the first solution is Se, Na 2 Se, K 2 Se, Ca 2 Se, (CH 3 ) 2 Se, Se02, SeCl 4 , H 2 Se0 3 , Na 2 S, K 2 S, Ca 2 S, (CH 3 ) 2 S, H 2 S0 4 , S, Na 2 S 2 0 3 , NH 2 S0 3 H and one selected from the group consisting of their hydrates Above or as organic matter, thiourea, thioacetamide, and
  • It may be one or more selected from the group consisting of sdenourea.
  • salts which are components of the second, third, and fourth solutions, include chloride, nitrate, nitrite, sulfate, and acetic acid.
  • the selection from the group consisting of salts, sulfites, acetylacetonates and hydroxides can be one or more of the forms,
  • tin (Sn) salts divalent and tetravalent salts are not limited and can be used.
  • the Group VI source is 0.5 moles or more, more specifically 0.5 moles, for 1 mole of copper (Cu) salt. It can be included in the desired composition ratio within the range of 4 moles.
  • the group VI source is out of the above range and contains less than 0.5 mole, it is impossible to provide sufficient group VI elements, so that stable phases such as CuS (Se) or Cu 2 S (Se) cannot be formed. Changes in the process or the problem of oxidizing the separated metals is not desirable.
  • the copper (Cu) -containing chalcogenide particles may be mixed with a third solution containing tin (Sn) salts to form a first shell on the surface thereof.
  • the amounts of tin (Sn) -containing chalcogenide and zinc (Zn) -containing chalcogenide contained in the material constituting the shell are determined to synthesize particles having a three-layer structure having the above composition ratio.
  • the concentration of tin (Sn) salt constituting the first shell can be determined in a range in which the molar ratio of tin (Sn) / copper (Cu) is 0.5 to 3, and the concentration of zinc (Zn) salt constituting the first shell is zinc.
  • the molar ratio of (Zn) / copper (Cu) can be determined in a range of 0.6 to 3.
  • first shell and the second shell may each include tin (Sn) -containing chalcogenide or zinc (Zn) -containing chalcogenide, and the first shell includes tin (Sn) -containing chalcogenide.
  • the second shell contains zinc (Zn) -containing chalcogenide, and the concentration of zinc (Zn) salt constituting the second shell to synthesize three-layer particles having the above composition ratio is zinc (Zn) / copper (Cu).
  • the molar ratio can be determined in the range of 0.6 to 3, and the concentration of tin (Sn) salts constituting the second shell is tin (Sn) / copper (if the first shell contains zinc (Zn) -containing chalcogenides).
  • the molar ratio of Cu) can be determined in a range of 0.5 to 3. .
  • An additional group VI source may be added to resolve partial shortage of group VI elements when forming the CZTS layer, wherein the group VI source is added by taking into account the amount of group VI elements remaining in each process.
  • the present invention provides a method for manufacturing a thin film including a light absorption layer based on nanoparticles having a three-layer core-shell structure.
  • the nanoparticles in the above process (i) have a diameter of 25 nanometers to 300 nanometers
  • the solvent can be used without particular limitation as long as it is a general organic solvent.
  • Organic solvents selected from amides can be used alone or in combination with one or more organic solvents selected from them.
  • the alcohol-based solvent is ethanol, 1-propanol (1-propanol),
  • 2-amino-2-methyl-1-propane may be one or more mixed solvents selected from (2-amino-2-methyl-1-propanoI).
  • the amine solvent is triethyl amine, dibutyl amine, dipropyl amine, butylamine, ethanolamine,
  • DETA Diethylenetriamine
  • TETA Triethylenetetraine
  • Dibutylamine and It may be one or more mixed solvents selected from tris (2-aminoethyl) amine.
  • the thiol solvent is at least one mixed solvent selected from 1,2-ethanedithiol, pentanethiol, hexanethiol, and mercaptoethanol.
  • the alkane solvent may be one or more mixed solvents selected from hexane, heptane and octane.
  • the aromatic compounds solvents include toluene, xylene,
  • It may be one or more mixed solvents selected from nitrobenzene and pyridine.
  • the organic halides solvent is at least one selected from chloroform, methylene chloride, tetrachloromethane, dichloroethane, and chlorobenzene. It may be a mixed solvent.
  • the nitrile solvent may be acetonitrile.
  • the ketone solvent may be one or more mixed solvents selected from acetone, cyclohexanone, cyclopentanone, and acetylacetone.
  • the ether solvent is ethyl ether
  • It may be one or more mixed solvents selected from tetrahydrofurane, and 1,4-dioxane.
  • the sulfoxides solvent is 13MSO (dimethyl sulfoxide), and
  • It may be one or more mixed solvents selected from sulfolane.
  • the amide solvent is DMF (dimethyl formamide), and
  • It may be one or more mixed solvents selected from n-methyl-2-pyrrolidone (NMP),
  • the ester solvent is ethyl lactate
  • It may be one or more mixed solvents selected from r-butyrolactone, and ethyl acetoacetateosis.
  • the carboxylic acid solvent may be selected from propionic acid, hexanoic acid, meso-2,3-dimercaptosuccinic acid, and thiolactic acid. It may be one or more mixed solvents selected from thiolactic acid and thioglycolic acid.
  • solvents may be one example and are not limited thereto.
  • it may be prepared by further adding an additive to the ink of step (i).
  • the additives are, for example, dispersants, surfactants, polymers, binders, crosslinkers, emulsifiers, antifoaming agents, desiccants, fillers, extenders, thickeners, film conditioners, antioxidants, glidants, leveling additives, and corrosion agents. May be one or more selected from the group consisting of inhibitors, specifically polyvinylpyrrolidone (PVP), Polyvinylalcohol, Anti-terra 204, Antitera
  • PVP polyvinylpyrrolidone
  • Polyvinylalcohol Anti-terra 204
  • Antitera Antitera
  • Anti-terra 205 (Anti-terra 205), ethyl cellulose, and
  • It may be one or more selected from the group consisting of DispersBYKl lO.
  • the method of forming the coating layer of step (ii) may include, for example, wet coating, spray coating, spin coating, doctor blade coating, contact printing, upper feed reverse printing, and lower printing.
  • Feed reverse printing, nozzle feed reverse printing, gravure printing, micro gravure printing, reverse micro gravure printing, lor coating, slot die ) Can be any one selected from the group consisting of coating, capillary coating, ink jet printing, jet deposition and spray deposition.
  • the heat treatment of the above process (Hi) can be performed at a temperature in the range of 350 to 900 degrees Celsius.
  • selenization process may be included to manufacture thin film of higher density solar cell, and the selenization process can be accomplished by various methods.
  • step (iii) above is performed under conditions in which S or Se is present.
  • the condition in which the S or Se element is present is possible by supplying gas in the form of H 2 S or 3 ⁇ 4Se, or by heating Se or S to a gas.
  • step (iii) is performed.
  • the lamination may be made by a solution process or may be made by a deposition method.
  • the present invention also provides a thin film manufactured by the above method.
  • the thin film may have a thickness in the range of 0.5 / m to 3.0 / m.
  • the thickness of the thin film may be 0.5 to 2.5 ions.
  • the thickness of the thin film is less than 0.5 jum, the density and amount of the light absorbing layer may not be sufficient to obtain a desired photoelectric efficiency. If the thin film exceeds 3.0 // m, the carrier may move. As the distance increases, the probability of recombination increases, which leads to a decrease in efficiency.
  • the present invention provides a thin film solar cell manufactured using the thin film.
  • XRD 4 is X-ray diffraction (XRD) of CuS nanoparticles formed in Preparation Example 14.
  • FIG. 5 is an electron micrograph (SEM) of CuS—ZnS core-shell nanoparticles formed in Preparation Example 17;
  • Example 7 is an electron microscope of CuS-ZnS-SnS core-shell nanoparticles formed in Example 2
  • Example 8 is an XRD (Xray diffraction) graph of CuS—ZnS—SnS core-shell nanoparticles formed in Example 2;
  • FIG. 9 is a photograph of CuS-ZnS-SnS core-shell nanoparticles formed in Example 2 with a transmission electron microscope (TEM, TEM-EDX); FIG.
  • Example 10 is a transmission electron of the CuS-ZnS-SnS nanoparticles formed in Example 2
  • FIG. 11 is an electron micrograph (SEM) photograph of the CZTSSe thin film prepared in Example 3.
  • SEM electron micrograph
  • CuS nanoparticles were prepared by centrifugation.
  • CuS nanoparticles were prepared by centrifugation.
  • DMF dimethyl formamide
  • Nanoparticles were prepared.
  • Example 19 The nanoparticles synthesized in Example 19 were mixed with a common solvent composed of an alcoholic solvent.
  • the ink was prepared by dispersing, and then coated on a glass substrate coated with molybdenum (Mo). After the coating film was dried, it was heated together with the Se-deposited glass substrate so that the Se atmosphere could be formed. Rapid thermal annealing (RTA) at 575 degrees Celsius produced CZTSSe based thin films.
  • RTA Rapid thermal annealing
  • CZTS solar cells by using the particles of the structure as precursors, and when manufacturing thin films using them as precursors, all elements essential to CZTS exist in the micro-region of several hundred nanometers, and they exist in the desired ratio. This allows not only to provide a good film quality in a short RTA process, but also to ensure the overall compositional uniformity of the thin film, making it easier to move electrons, making solar cells with improved overall light conversion efficiency.
  • a core including a copper (Cu) -containing chalcogenide, and a tin (Sn) -containing chalcogenide (i) a tin (Sn)
  • the three-layer core-shell structure since the nanoparticles of the three-layer core-shell structure are stable to oxidation and have excellent reaction properties, when the thin film is manufactured using the same, the three-layer core-shell structure not only provides a good film quality but also Cu in one particle. It contains all of Sn, Zn, S or Se, so that the overall composition uniformity of the thin film can be secured. As a result, the photovoltaic efficiency of the solar cell according to the present invention is improved.

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Abstract

본 발명은 태양전지의 광흡수층을 형성하는데 사용되는 3층 코어-쉘구조의 나노 입자로서, 구리 (Cu) 함유 칼코게나이드를 포함하는 코어 (core)와, (1)주석 (Sn)함유 칼코게나이드를 포함하는 제 1쉘 (shell) 및 아연 (Zn) 함유 칼코게나이드를 포함하는 제 2 쉘 (shell);또는 (ii)아연(Zn) 함유 칼코게나이드를 포함하는 제 1쉘 (shell) 및 주석(Sn) 함유 칼코게나이드를 포함하는 제 2쉘 (shell);로 이루어진 것을 특징으로 하는 3층코어-쉘 구조의 나노입자 및 이의 제조방법에 관한 것이다.

Description

명세서
발명의명칭:태양전지광흡수층제조용 3층코어-쉘나노입자및 이의제조방법
기술분야
[1] 본발명은태양전지광흡수층제조용 3층코어-쉘나노입자및이의제조
방법에관한것이다.
배경기술
[2] 태양전지는개발초기때부터비싼제조과정의광흡수층및반도체물질로서 규소 (Si)를사용하여제작되어왔다.태양전지를더욱경제적으로산업에이용 가능하도록제조하기위해,박막태양전지의구조물로저비용의
CIGS (구리-인듬-갈륨-설포-다이-셀레나이드， Cu(In, Ga)(S, Se)2)와같은광흡수 물질을이용한제품이개발되어왔다.상기 CIGS계의태양전지는전형적으로 후면전극층， n-형접합부，및 P-형흡광층으로구성된다.이렇게 CIGS층이 기재된태양전지는 19%를초과하는전력변환효율을갖는다.그러나， CIGS계의박막태양전지에대한잠재성에도불구하고，인듐 (In)의원가와 공급량부족으로인하여 CIGS계의광흡수층을이용한박막태양전지의 광범위한용도및적용성에주요한장애가되고있는바, In-free나 In-less의저가 범용원소를이용하는태양전지개발이시급한실정이다.
[3] 따라서，최근에는상기 CIGS계의광흡수층에대한대안으로초저가금속
원소인구리,아연，주석，황，또는샐레늄원소를포함하는 CZTS(Cu2ZnSn(S,Se)4 )계태양전지가주목받고있다,상기 CZTS는약 1.0내지 1.5eV의직접밴드 갭 (direct band gap)및 104 cm-'이상의흡수계수를갖고있고,상대적으로 매장량이풍부하고가격이저렴한 Sn과 Zn을사용하는장점을가지고있다.
[4] 1996년에처음 CZTS해테로-접합 PV전지가보고되었지만，현재까지도
CZTS를기반으로한태양전지의기술은 CIGS의태양전지의기술보다뒤처져 있고， CZTS전지에대한광전효율은 10%이하로 CIGS의그것에비해아직많이 부족한상태이다. CZTS의박막은스퍼터링 (sputtering),하이브리드
스퍼터링 (hybrid sputtering),필스레이저 (pulse laser)증착법，분무열분해법， 전착 /열황화 (thermal sulfurization), E-빔 (E-beam) Cu/Zn/Sn/열황화,및
졸-겔 (sol-gel)의방법들을이용하여제조되어왔다.
[5] 제조방법과관련하여， WO2007-134843는진공방식의스퍼터링방법으로 Cu,
Zn, Sn을동시또는순차적으로적층한후， S또는 Se분위기하에서열처리하여 CZTS층을형성하는방법을개시하고있고,일부논문 (Phys, Stat. Sol. C. 2006, 3, 2844. / Prog. Photovolt: Res. Appl. 2011; 19:93-96)에서는진공방식의동시 증발법으로 Cu, Zn, Sn, S또는 Se를동시에기재상에증착시켜 CZTS층을 형성하는방법을개시하고있다.그러나，상기기술들은비교적잘제어된 상태로증착이가능하다는장점은있으나，고가의장비를사용하므로공정 비용이많이들어생산에한계가있다.
[6] 한편， PCT/US/2010-035792에서는 CZTS/Se전구체입자를포함하는잉크를 이용하여기재상에열처리하여박막을형성시킨내용을개시하고있는데，상기 CZTS전구체입자를형성하는방법과관련하여,저널 JACS, 2009， 131,
11672에서는고열주입 (hot injection)법으로 Cu, Sn,및 Zn의전구체를포함하는 용액과 S또는 Se가포함된용액을고온에서흔합하여 CZTS나노입자를 형성하는방법을개시하고있고, US2011-0097496은 CZTS층형성용전구체로 하이드라진 (hydrazine)에 Cu, Zn, Sn염을과량의 S또는 Se과함께녹인것을 사용하고，후속공정에서열처리와셀렌화를통해 CZTS층을형성하는방법을 개시하고있다.그러나，고열주입법은안전성에문제가있고,하이드라진을 이용한용액공정은과량의 S또는 Se을포함하는칼코겐 (chalcogen)화합물이 함유된하이드라진이독성이강하고반웅성이큰잠재적폭발성의용매이므로 높은위험성을내재하고있고，이를취급하기가용이하지않아공정의어려움이 있다.
[7] 따라서,기존 CZTS층의제조공정보다저렴하고，안전한제조방법으로산화에 안정할뿐아니라높은효율의광흡수층을형성할수있는박막태양전지에대한 기술의필요성이높은실정이다.
발명의상세한설명
기술적과제
[8] 본발명은상기와같은종래기술의문제점과과거로부터요청되어온기술적 과제를해결하는것을목적으로한다.
[9] 본출원의발명자들은심도있는연구와다양한실험을거듭한끝에,구리 (Cu) 함유칼코게나이드를포함하는코어 (core)와, (i)주석 (Sn)함유칼코게나이드를 포함하는제 1쉘 (shell)및아연 (Zn)함유칼코게나이드를포함하는제 2쉘 (shell); 또는 (ii)아연 (Zn)함유칼코게나이드를포함하는제 1쉘 (shell)및주석 (Sn)함유 칼코게나이드를포함하는제 2쉘 (shell);로이루어진 3층코어-쉘구조의나노 입자를사용하여광흡수층을제조하는경우，저렴하고안전한공정이가능하여 생산성을높일수있을뿐만아니라，박막전체적으로조성이균일하고,산화에 안정한박막을제공할수있고,높은밀도의 CZTS계태양전지용광흡수층을 성장시켜광전효율을향상시킬수있는것을확인하고,본발명을완성하기에 이르렀다.
과제해결수단
[10] 따라서,본발명에따른 3층코어-쉘구조의나노입자는태양전지의
광흡수층을형성하는 3층코어-쉘구조의나노입자로서，구리 (Cu)함유 칼코게나이드를포함하는코어 (core)와，
[11] (i)주석 (Sn)함유칼코게나이드를포함하는제 1쉘 (shell)및아연 (Zn)함유 칼코게나이드를포함하는제 2쉘 (shell);또는
[12] (ii)아연 (Zn)함유칼코게나이드를포함하는제 1쉘 (shell)및주석 (Sn)함유 칼코게나이드를포함하는제 2쉘 (shell);
[13] 로이루어진것을특징으로한다.
[14] 여기서 '코어 (core)'는여러가지종류의조성을가진나노입자에서주로
증심부에위치하는물질로서 1차적으로합성된입자를의미하고, '쉘 (shell)'은 코어로구분되는입자의표면부에코어를이루는입자와다른종류의입자가 합성되면서코어의표면전부또는일부를감싸는경우를의미한다.즉,쉘은 코어의표면전부를감싸는경우뿐아니라코어의적어도일부를감싸고있는 경우를포함한다.이렇게합성된코어-쉘구조의입자는수백나노미터의 미시영역에서코어를증심으로쉘을이루는다른두종류의입자들이각각 공존하여광흡수층형성에필요한 3가지원소의조성비를조절하기용이한 잇점이있다.
[15] 또한，여기서 '칼코게나이드'는 VI족원소，예를들어，황 (S)및 /또는
셀레늄 (Se)을포함하는물질을의미한다.
[16] 따라서，하나의구체적인예에서，상기구리 (Cu)함유칼코게나이드는 CuS, Cux S(1.7<x<2.0), CuSe,및 CuySe(1.7≤y≤2.0)로이루어진군으로부터선택되는하나 이상일수있고，상세하게는 Cu2S, CuS, Cu2Se,및 CuSe로이루어지는군으로부터 선택되는하나이상일수있으며，더욱상세하게는 CuS및 /또는 CuSe일수있다.
[17] 또한，주석 (Sn)함유칼코게나이드는 SnS,및 /또는 SnSe일수있고,아연 (Zn) 함유칼코게나이드는 ZnS,및 /또는 ZnSe일수있다.
[18]
[19] 일반적으로， CZTS결정형나노입자를사용하여 CZTS박막을형성하는경우, 이미형성된결정이작기때문에이후박막을형성하는과정에서결정의크기를 키우기가힘들고,이와같이각각의그레인 (grain)이작은경우에는경계면이 늘어나게되고，경계면에서생기는전자의손실때문에효율이떨어질수밖에 없다 · ,
[20] 그에비해， Cu, Zn, Sn을포함하지만 CZTS결정형태가아니고，서로분리되어 존재하는 Cu, Zn, Sn등의원소가이차상을거쳐 CZTS를형성하는경우에는, 박막의형성과정에서각각의원소들이재배치되면서결정이성장하기때문에 막밀도향상，결정크기향상을유도할수있다.
[21] 따라서，박막에사용되는나노입자는 Cu, Zn, Sn을포함하되 , CZTS결정이 아닌형태를취해야하는데，단일금속원소로구성된금속나노입자는 산화되기쉽고,이후과량의 Se와높은온도를이용한산소의제거공정이 필요하다는단점이있다.
[22] 이에,본출원의발명자들은심도있는연구를거듭한끝에，금속과
칼코게나이드가결합된형태의나노입자를활용하는경우， CZTS박막을 형성하기위한고온공정에서칼코게나이드원소를적절히공급하여산화를 방지할수있음을밝혀내었다.
[23] 더욱이，한개의나노입자에 Cu, Zn, Sn을한꺼번에포함하는경우에는각각의 원소를포함하는여러종류의나노입자를사용하는경우와비교하여조성의 균일성을확보할수있는데，코어-쉘구조의경우에는코어와쉘을구성하는 물질의비율을조절하여입자내 Cu, Zn, Sn의비율을조절하기쉽기때문에최종 CZTS박막의조성비역시조절하기쉬운바，다양한조성비의 CZTS박막의 형성에사용또한가능하다.
[24] 한편，구조와관련하여， Cu, Zn, Sn의이온화경향차이때문에본발명에따른 구조이외의순서를가지는 3층코어-쉘구조의나노입자는제조가어려운데 비해특별한장점을기대하기힘돌다.예를들어,아연 (Zn)함유칼코게나이드의 코어입자에구리 (Cu)함유칼코게나이드의쉘을제조하기위해 Cu염을 사용하는경우， Zn과 Cu의이은화경향차이때문에코어-쉘구조의나노입자를 제조시，아연 (Zn)함유칼코게나이드코어의 Zn일부가이온화되면서 Cu가 환원되기쉽고，따라서아연 (Zn)함유칼코게나이드코어와구리 (Cu)함유 칼코게나이드쉘이명확히만들어지지않고 Cu, Zn，등이불균일하게분포된 섞여있는형태가형성되기쉬우며 ,이온화된 Zn일부가산소와결합하여 산화물을생성할수있는문제가있다.
[25] 하나의구체적인예에서，상기코어의입경은 20나노미터내지 200나노미터일 수있다.상기범위를벗어나구리 (Cu)함유칼코게나이드를포함하는코어의 크기가너무큰경우에는쉘까지형성한코어-쉘구조의나노입자크기가너무 커져 1마이크로미터내지 2마이크로미터의두께를갖는최종박막에서의 입자들사이의공극이커지므로바람직하지않고，코어의크기가너무작은 경우에는입자들사이의응집이쉬울뿐만아니라，최종박막이적절한조성비를 갖게하기위하여코어의표면을감싸는쉘을얻기어려운바，바람직하지않다.
[26] 한편,상기제 1쉘및제 2쉘의중량은，코어를형성한후,또는제 1쉘을
형성한후,그표면에제 1쉘또는제 2쉘을형성시킬때의반웅시간,반응온도， 반웅물의눔도둥에의해조절되는데,이를조절하여형성시키는쉘을구성하는 물질에포함되는아연칼코게나이드의중량은코어를구성하는구리
칼코게나이드의증량부 100대비 35내지 100증량부범위내인것이
바람직하고,주석칼코게나이드의경우구리칼코게나이드의중량부 100대비
40내지 65증량부범위를갖는것이바람직하다.
[27] 구체적으로，상기제 1쉘및제 2쉘의중량은목표하는 CZTS박막의전체적인 조성비와코어와의조성비를감안하여결정됨이바람직한데,일반적으로， CZTS 박막의조성비는 Cu： Zn： Sn=l.5-2.5： 0.9-1.5： 1정도의조성비를가지므로， 금속나노입자와혼합하여 CZTS박막을형성하는경우,상기 3층코어-쉘 구조의나노입자는 Cu： Zn=0.3~1.3： 0.9~1.5의조성비를가질수있고,따라서， 상기코어의입경이 20나노미터내지 200나노미터일때，제 1쉘및제 2쉘은 상기범위의물질올포함할수있다. [28] 본발명은또한,상기 3층코어-쉘구조의나노입자의제조방법을제공하는 바,상기제조방법은,
[29] (i)황 (S),또는샐레늄 (Se),또는황 (S)및셀레늄 (Se)을포함하는화합물로
이루어진군에서선택되는 1종이상의 VI족소스를포함하는제 1용액을 준비하는과정 ;
[30] (ii)구리 (Qi)염을포함하는제 2용액과주석 (Sn)염을포함하는제 3용액및 아연 (Zn)염을포함하는제 4용액을준비하는과정；
[31] (iii)상기제 1용액과제 2용액을흔합하여혼합물을제조하고,반웅시켜
구리 (Cu)함유칼코게나이드코어입자를합성하는과정 ;
[32] (iv)상기과정 (iii)의코어입자를포함하는생성물에상기제 3용액이나 4 용액을혼합하여제 1쉘을형성하는과정；
[33] (V)상기과정 (iv)의제 1쉘이형성된코어-쉘구조의나노입자를포함하는 생성물에상기제 4용액이나제 3용액을혼합하여제 2쉘을형성하여 3충 코어-쉘구조의나노입자를합성한후，정제하는과정 ;
[34] 을포함하는것을특징으로한다.
[35] 하나의구체적인예에서，상기제 1용액내지제 4용액의용매는서로
독립적으로,물,메탄을 (methanol),에탄을 (ethanol),글리콜류용매，
오레일아민 (oleylamine),디메틸설폭사이드 (dimethyl sulfoxide),및
디메틸포름아마이드 (dimethyl formamide)로이루어진군에서선택되는하나 이상일수있다.
[36] 상기글리콜류용매는한정되지않으나，예를들어 ,
에틸렌글리콜 (ethyleneglycol),디에틸렌글리콜 (diethylene glycol), NMP, 디에틸렌글리콜모노에틸에테르 (diethylene glycol mono ethyl ether: DEGMEE)및 트리에틸렌글리콜 (triethylene glycol)으로이루어진군에서선택되는어느하나일 수있다.
[37] 상기와같이，본발명에따른 3층코어-쉘구조의나노입자의제조방법은용액 공정으로이루어지므로공정비용을낮출수있고,용액올제조하기위해유독한 물질을사용하지않으며，캡핑제의사용을줄여 CZTS박막형성시탄소의 잔여물의감소도가능하다.
[38] 하나의구체적인예에서，상기제 1용액에포함되는 VI족소스는 Se, Na2Se, K2 Se, Ca2Se, (CH3)2Se, Se02, SeCl4, H2Se03, Na2S, K2S, Ca2S, (CH3)2S, H2S04, S, Na2S2 03, NH2S03H및이들의수화물로이루어진군에서선택되는하나이상이거나， 유기물로서,티오요소 (thiourea),티오아세트아미드 (thioacetamide),및
셀레노유레아 (sdenourea)로이루어진군에서선택되는하나이상일수있다.
[39] 하나의구체적인예에서，상기제 2용액，제 3용액,및제 4용액에포함되는 성분인염은，염화물 (chloride),질산염 (nitrate),아질산염 (nitrite),황산염 (sulfate), 아세트산염 (acetate),아황산염 (sulfite),아세틸아세토네이트염 (acetylacetonate)및 수산화물 (hydroxide)로이루어진군에서선택돠는하나이상의형태일수있고, 주석 (Sn)염의경우에는 2가및 4가의염이한정되지아니하고모두사용 가능하다.
[40] 한편，상기과정 (iii)에서와같이제 1용액에제 2용액을흔합하는경우,상기 VI족소스는구리 (Cu)염 1몰에대해 0.5몰이상，상세하게는， 0.5몰내지 4몰의 범위내에서소망하는조성비로포함될수있다.
[41] 상기범위를벗어나 VI족소스가 0.5몰미만으로포함되는경우， VI족원소의 충분한제공이불가능하므로 CuS(Se)나, Cu2S(Se)와같은안정한상이형성되지 못하는바，이후공정에서상이변하거나분리된금속이산화될수있는문제가 있어바람직하지않다.
[42] 또한， 4몰을초과하여포함되는경우에는의도하지않은 VI족원소가생성될 확률이증가하고，박막을제조하기위한열처리공정에서 VI족소스가 증발하면서최종박막에공극미과도하게형성될수있는확률이증가하는 문제가있을수있다.
[43] 구체적으로，구리 (Cu)함유칼코게나이드입자는그표면에제 1쉘 (shell)을 형성하기위해,주석 (Sn)염을포함하는제 3용액과흔합될수있고，
아연 (Zn)염을포함하는제 4용액과혼합될수있다.
[44] 이때，상기흔합시，주석 (Sn)염의농도또는아연 (Zn)염의농도에의
[45] 해서도쉘을구성하는물질에포함된주석 (Sn)함유칼코게나이드와아연 (Zn) 함유칼코게나이드의양이결정되는바,상기조성비의 3층구조의입자를 합성하기위해서，'제 1쉘을구성하는주석 (Sn)염의농도는주석 (Sn)/구리 (Cu)의 몰비가 0.5내지 3이되는범위에서정해질수있고,제 1쉘을구성하는 아연 (Zn)염의농도는아연 (Zn)/구리 (Cu)의몰비가 0.6내지 3가되는범위에서 정해질수있다.
[46] 또한，제 1쉘및제 2쉘은각각주석 (Sn)함유칼코게나이드또는아연 (Zn)함유 칼코게나이드를포함할수있으며,제 1쉘이주석 (Sn)함유칼코게나이드를 포함하는경우제 2쉘은아연 (Zn)함유칼코게나이드를포함하며,상기 조성비를갖는 3층입자를합성하기위해서제 2쉘을구성하는아연 (Zn)염의 농도는아연 (Zn)/구리 (Cu)의몰비가 0.6내지 3이되는범위에서정해질수있고, 제 1쉘이아연 (Zn)함유칼코게나이드를포함하는경우제 2쉘을구성하는 주석 (Sn)염의농도는주석 (Sn)/구리 (Cu)의몰비가 0.5내지 3이되는범위에서 정해질수있다. .
[47] 하나의구체적인예에서，제 3용액의혼합시또는제 4용액의혼합시，추후
CZTS층을형성하는경우의 VI족원소의부분적인부족을해결하기위해추가로 VI족소스를첨가할수있고，이때，상기 VI족소스는각각의공정에서잔류하는 VI족원소의양을감안하여첨가될수있다.
[48] 한편,본출원의발명자들은,상기와같이제조된 3층코어-쉘구조의나노
입자들을사용하여박막을제조하는경우，양질의막질을제공할수있을뿐 아니라，박막의전체적인조성균일성을확보할수있음을확인하였다. [49] 따라서，본발명은상기 3층코어-쉘구조의나노입자에기반한광흡수층을 포함하는박막의제조방법을제공한다.
[50] 본발명에따른박막의제조방법은，
[51] (i) 3층코어-쉘구조의나노입자를용매에분산하여잉크를제조하는과정;
[52] (ii)전극이형성된기재상에상기잉크를코팅하는과정 ;및
[53] (iii)상기전극이형성된기재상에코팅된잉크를건조한후열처리하는과정； [54] 을포함하는것을특징으로한다.
[55] 상기과정 (i)의나노입자는 25나노미터내지 300나노미터의직경을갖는것이 바람직하며,용매는일반적인유기용매라면특별히제한없이사용할수있는데 알칸계 (alkanes),알켄계 (alkenes),알킨계 (alkynes),방향족화합물계 (aromatics), 케톤계 (ketons),니트릴계 (nitriles),에테르계 (ethers),에스테르계 (esters), 유기할로겐화물계 (organic halides),알코올계 (alcohols),아민계 (amines), 티올계 (thiols),카르복실산계 (carboxylic acids),수소화인계 (phosphines), 아인산계 (phosphites),인산염계 (phosphates),술폭시화물계 (sulfoxides),및 아미드계 (amides)증에서선택된유기용매를단독으로사용하거나이들중에서 선택된하나이상의유기용매가혼합된형태로사용할수있다.
[56] 구체적으로,상기알코올계용매는에탄올， 1-프로판올 (1-propanol),
2-프로판올 (2-propanol), 1-펜타놀 (1-pentanol), 2-펜타놀 (2-pentanol),
1-핵사놀 (l-hexanol), 2-핵사놀 (2-hexanol), 3-핵사놀 (3-hexanol),헵타놀 (heptanol), 욱타놀 (octanol), EG(ethylene glycol), DEGMEE(diethylene glycol monoethyl ether), EGMME(ethylene glycol monomethyl ether), EGMEE(ethylene glycol monoethyl ether), EGDME(ethylene glycol dimethyl ether), EGDEE(ethylene glycol diethyl ether), EGMPE(ethylene glycol monopropyl ether), EGMBE(ethylene glycol monobutyl ether), 2-메틸 -1-프로판을 (2-methyl-l-propanol),
시클로펜탄을 (cyclopentanol),시클로헥산올 (cyclohexanol), PGPE(propylene glycol propyl ether), DEGDME(diethylene glycol dimethyl ether), 1 ,2-PD( 1 ,2-propanediol), 1,3-PD(1 ^-propanediol), 1 ,4-BD(l ,4-butanediol), 1,3-BD(1 ,3-butanediol), 알파테르피네을 (α-terpineol), DEG (diethylene glycol),글리세를 (glycerol),
2-에틸아미노에탄올 (2-(ethylamino)ethanol),
2- (메틸아미노)에탄올 (2-(methylamino)ethanol),및
2-아미노 -2-메틸 -1-프로판을 (2-amino-2-methyl-l-propanoI)증에서선택되는하나 이상의흔합용매일수있다.
[57] 상기아민계용매는트리에틸아민 (triethyl amine),디부틸아민 (dibutyl amine), 디프로필아민 (dipropyl amine),부틸아민 (butylamine),에탄을아민 (ethanolamine),
DETA(Diethylenetriamine), TETA(Triethylenetetraine),
트리에탄을아민 (Triethanolamine), 2-아미노에틸피페라진 (2-aminoethyl piperazine), 2-하드록시에틸피페라진 (2-hydroxyethyl piperazine),
다이부틸아민 (dibutylamine),및 트리스 (2-아미노에틸)아민 (tris(2-aminoethyl)amine)중에서선택되는하나이상의 흔합용매일수있다.
[58] 상기티올계용매는 1,2-에탄디티올 (1,2-ethanedithiol),펜탄티올 (pentanethiol), 핵산티올 (hexanethiol)，및메르캅토에탄올 (mercaptoethanol)증에서선택되는 하나이상의혼합용매일수있다.
[59] 상기알칸계 (alkane)용매는핵산 (hexane),헵탄 (heptane),옥탄 (octane)중에서 선택되는하나이상의흔합용매일수있다.
[60] 상기방향족화합물계 (aromatics)용매는를루엔 (toluene),자일렌 (xylene),
니트로벤젠 (nitrobenzene)，피리딘 (pyridine)중에서선택되는하나이상의혼합 용매일수있다.
[61] 상기유기할로겐화물계 (organic halides)용매는클로로포름 (chloroform),메틸렌 클로라이드 (methylene chloride),테트라클로로메탄 (tetrachloromethane), 디클로로에탄 (dichloroethane),및클로로벤젠 (chlorobenzene)증에서선택되는 하나이상의흔합용매일수있다.
[62] 상기니트릴계 (nitrile)용매는아세토니트릴 (acetonitrile)일수있다.
[63] 상기케론계 (ketone)용매는아세톤 (acetone)，시클로핵사논 (cyclohexanone), 시클로펜타논 (cyclopentanone),및아세틸아세톤 (acetyl acetone)증에서선택되는 하나이상의흔합용매일수있다.
[64] 상기에테르계 (ethers)용매는에틸에테르 (ethyl ether),
테트라하이드로퓨란 (tetrahydrofurane),및 1,4-다이옥산 (1,4-dioxane)중에서 선택되는하나이상의혼합용매일수있다.
[65] 상기술폭시화물계 (sulfoxides)용매는 13MSO(dimethyl sulfoxide),및
술포란 (sulfolane)증에서선택되는하나이상의혼합용매일수있다.
[66] 상기아미드계 (amide)용매는 DMF(dimethyl formamide),및
NMP(n-methyl-2-pyrrolidone)중에서선택되는하나이상의혼합용매일수있다,
[67] 상기에스테르계 (ester)용매는에틸락테이트 (ethyl lactate),
r-부틸로락톤 (r-butyrolactone),및에틸아세토아세테이트 (ethyl acetoacetate) 증에서선택되는하나이상의흔합용매일수있다.
[68] 상기카르복실산계 (carboxylic acid)용매는프로피온산 (propionic acid),핵산 산 (hexanoic acid),메소 -2,3-디메르갑토숙신산 (meso-2,3-dimercaptosuccinic acid), 티오락틱산 (thiolactic acid),및티오글리콜산 (thioglycolic acid)중에서선택되는 하나이상의흔합용매일수있다.
[69] 그러나,상기용매들은하나의예시일수있으며이에한정되지않는다.
[70] 경우에따라서는，상기과정 (i)의잉크에첨가제를더첨가하여제조될수있다.
[71] 상기첨가제는예를들어,분산제，계면활성제，중합체,결합제,가교결합제， 유화제，소포제，건조제，충전제,증량제,증점화제，필름조건화제，항산화제, 유동제,평활성첨가제，및부식억제제로이루어진군에서선텍되는어느하나 이상일수있고，상세하게는폴리비닐피로리돈 (polyvinylpyrrolidone: PVP), 폴리비닐알코올 (Polyvinylalcohol),안티테라 204(Anti-terra 204),안티테라
205(Anti-terra 205),에틸셀를로오스 (ethyl cellulose),및
디스퍼스 BYKl lO(DispersBYKl lO)으로이루어진군에서선택되는어느하나 이상일수있다.
[72] 상기과정 (ii)의코팅층을형성하는방법은,예를들어，습식코팅 ,분무코팅, 스핀코팅，닥터블레이드 (doctor blade)코팅,접촉프린팅，상부피드리버스 (feed reverse)프린팅，하부피드리버스 (feed reverse)프린팅,노즐피드리버스 (nozzle feed reverse)프린팅，그라비어 (gravure)프린팅，마이크로그라비어 (micro gravure) 프린팅，리버스마이크로그라비어 (reverse micro gravure)프린팅,를러코팅,슬롯 다이 (slot die)코팅，모세관코팅，잉크젯프린팅,젯 (jet)침착,분무침착으로 이루어진군에서선택되는어느하나일수있다.
[73] 상기과정 (Hi)의열처리는섭씨 350내지 900도범위의온도에서수행될수
있다.
[74] 한편,더욱높은밀도의태양전지의박막을제조하기위해서는셀렌화공정이 포함될수있고,상기샐렌화공정은다양한방법에의해이루어질수있다.
[75] 첫번째예에서，상기과정 (i)에서금속칼코게나이드나노입자또는금속
칼코게나이드나노입자혼합물과함께 S및 /또는 Se를입자형태로용매에 분산하여잉크를제조하고，과정 (Hi)의열처리를통함으로써달성될수있다.
[76] 두번째예에서 ,상기과정 (iii)의열처리를 S또는 Se가존재하는조건에서
수행함으로써달성될수있다.
[77] 상세하게는，상기 S또는 Se원소가존재하는조건은 H2S또는 ¾Se의가스 형태로공급하거나， Se또는 S를가열하여기체로공급함으로써가능하다.
[78] 세번째예에서，상기과정 (ii)이후에 S또는 Se를적층한후과정 (iii)을
진행하여달성될수있다.상세하게는,상기적층은용액공정에의하여 이루어질수있고증착방법에의해이루어질수도있다.
[79] 본발명은또한상기방법으로제조된박막을제공한다.
[8이 상기박막은 0.5 / m내지 3.0 / m의범위내에서두께를가질수있으며，더욱
상세하게는박막의두께는 0.5 내지 2.5 ion일수있다.
[81] 박막의두께가 0.5 jum미만인경우에는광흡수층의밀도와양이층분치못해 소망하는광전효율을얻을수없고,박막이 3.0 //m를초과하는경우에는， 전하운반자 (carrier)가이동하는거리가증가함에따라재결합 (recombination)이 일어날확를이높아지므로이로인한효율저하가발생하게된다.
[82] 더나아가,본발명은상기박막을사용하여제조되는박막태양전지를
제공한다.
[83] 박막의태양전지를제조하는방법은당업계에이미알려져있으므로본
명세서에는그에대한설명을생략한다.
도면의간단한설명 [84] 도 1은제조예 13에서형성된 CuS나노입자의전자현미경 (SEM)사진이다;
[85] 도 2은제조예 13에서형성된 CuS나노입자의 XRD(X-ray diffraction)
그래프이다;
[86] 도 3는제조예 14에서형성된 CuS나노입자의전자현미경 (SEM)사진이다;
[87] 도 4는제조예 14에서형성된 CuS나노입자의 XRD(X-ray diffraction)
그래프이다;
[88] 도 5는제조예 17에서형성된 CuS-ZnS코어-쉘나노입자의전자현미경 (SEM) 사진이다;
[89] 도 6은제조예 17에서형성된 CuS-ZnS코어-쉘나노입자를투과식전자
현미경 (TEM, TEM-EDX)으로분석한사진이다;
[90] 도 7은실시예 2에서형성된 CuS-ZnS-SnS코어-쉘나노입자의전자현미경
(SEM)사진이다;
[91] 도 8은실시예 2에서형성된 CuS-ZnS-SnS코어-쉘나노입자의 XRD(Xray diffraction)그래프이다;
[92] 도 9는실시예 2에서형성된 CuS-ZnS-SnS코어-쉘나노입자를투과식전자 현미경 (TEM, TEM-EDX)으로분석한사진이다;
[93] 도 10은실시예 2에서형성된 CuS-ZnS-SnS나노입자를투과식전자
현미경 (TEM, TEM-EDX)으로분석한또다른사진이다;및
[94] 도 11은실시예 3에서제조된 CZTSSe박막의전자현미경 (SEM)사진이다. 발명의실시를위한형태
[95] 이하，본발명의실시예를참조하여설명하지만,하기실시예는본발명을 예시하기위한것이며,본발명의범주가이들만으로한정되는것은아니다.
[96]
[97] <제조예 1>
[98] CuS입자의합성
[99] 5 mm이의 Na2S을포함하는수용액 150 mL에 5 mm이의 Cu(N03)2를포함하는 수용액 100 mL을적가한후， 2시간동안교반하여반웅시키고，형성된입자를 원심분리법으로정제하여 CuS나노입자를제조하였다.
[100]
[101] <제조예 2>
[102] CuS입자의합성
[103] 5 mm이의 Cu(N03)2과 10 mm이의티오아세트아미드 (thioacetamide)를포함하는 수용액 200 mL을교반하며섭씨 80도이상으로가열하고，온도를유지하면서 3시간동안교반하여반웅시키고,형성된입자를원심분리법으로정제하여 CuS 나노입자를제조하였다.
[104]
[105] <제조예 3> [106] CuS ¾자의함성
[107] 5 mm이의 CuCl2을포함하는수용액 60 mL를섭씨 80도이상으로가열한다음， 10 mm이의티오아세트아미드 (thioacetamide)를포함하는수용액 60 mL를천천히 적가한후， 3시간동안교반하여반웅시키고,형성된입자를원심분리법으로 정제하여 CuS나노입자를제조하였다.
[108]
[109] <제조여 ] 4>
[110] CuS입자의합성
[111] 5 mm이의 Cu(N03)2을포함하는디에틸렌글리콜 (diethylene glycol: DEG)용액 60 mL을섭씨 60도이상으로가열한다음 10 mmol의
티오아세트아미드 (thioacetamide)를포함하는 DEG용액 60 mL을적가한후， 은도를유지하면서 1시간동안교반하여반웅시키고,형성된입자를
원심분리법으로정제하여 CuS나노입자를제조하였다.
[112]
[113] <제조예 5>
[114] CuS입자의합성
[115] 5 mm 의 0!( 03)2을포함하는 DEG용액 300 mL을섭씨 120도로가열한다음 10 mm이의티오아세트아미드 (thioacetamide)를포함하는 DEG용액 100 mL를 적가한후,섭씨 120도의온도를유지하면서 3시간동안교반하여반웅시키고, 형성된입자를원심분리법으로정제하여 CuS나노입자를제조하였다.
[116]
[117] <제조예 6>
[118] CuS 자의합성
[119] 5 mm 의 0 ( 03)2와 10 mm이의티오아세트아미드 (thioacetamide)를포함하는 에틸렌글리콜 (ethylene glycol: EG)용액 80 mL을섭씨 100도로가열한다음， 온도를유지하면서 3시간동안교반하여반응시키고,형성된입자를
원심분리법으로정제하여 CuS나노입자를제조하였다.
[120]
[121] <제조예 7>
[122] CuS입자의합성
[123] DEG용액 200 mL을섭씨 120도이상으로가열한다음 10 mm이의
티오아세트아미드 (thioacetamide)를포함하는 DEG용액 50 mL을적가한후, 5mm이의 Cu(N03)2을포함하는 DEG용액 50 mL을적가하고，온도를유지하면서 3시간동안교반하여반웅시키고,형성된입자를원심분리법으로정제하여 CuS 나노입자를제조하였다.
[124]
[125] <제조예 8>
[126] CuS입자의합성 [127] 5 mm이의 01 03)2을포함하는 EG용액 250 mL을섭씨 170도이상으로가열한 다음 10 mm이의티오아세트아미드 (thioacetamide)를포함하는 EG용액 50 mL을 적가한후，온도를유지하면서 3시간동안교반하여반웅시키고，형성된입자를 원심분리법으로정제하여 CuS나노입자를제조하였다.
[128]
[129] <제조예 9>
[130] CuS입자의합성
[131] 4 mm이의티오아세트아미드 (thioacetamide)를포함하는 DMSO(dimethyl
sulfoxide)용액 50 mL을섭씨 60도이상으로가열한다음， 2 ιηπωΐ의 Cu(OAc)2를 포함하는 DMSO(dimethyI sulfoxide)용액 50 mL을적가한후，온도를유지하면서 3시간동안교반하여반웅시키고，형성된입자를원심분리법으로정제하여 CuS 나노입자를제조하였다.
[132]
[133] <제조예 10>
[134] CuS입자의합성
[135] 디메틸포름아마이드 (dimethyl formamide: DMF)용액 200 mL을섭씨 120도 이상으로가열한다음 10 mm이의티오아세트아미드 (thioacetamide)를포함하는 DMF용액 50 mL을적가한후， 5 mm이의 Cu(N03)2을포함하는 DMF용액 50 mL을적가하고,온도를유지하면서 3시간동안교반하여반응시키고，형성된 입자를원심분리법으로정제하여 CuS나노입자를제조하였다.
[136]
[137] <제조예 11>
[138] CuS입자의합성
[139] 5 mm이의 01( 03)2을포함하는수용액 250 mL을섭씨 170도이상으로가열한 다음 10 mm이의티오아세트아미드 (thioacetamide)를포함하는 EG용액 50 mL을 적가한후，온도를유지하면서 3시간동안교반하여반응시키고,형성된입자를 원심분리법으로정제하여 CuS나노입자를제조하였다.
[140]
[141] <제조예 12>
[142] CuS입자의합성
[143] PVP 3 g이포함된 DEG용액 200 mL을섭씨 120도이상으로가열한다음 10 mm이의티보아세트아미드 (thioacetamide)를포함하는 DEG용액 50 mL를적가한 후， 5 mm이의 Cu(N03)2을포함하는 DEG용액 50 mL을적가하고，온도를 유지하면서 3시간동안교반하여반웅시키고，형성된입자를원심분리법으로 정제하여 CuS나노입자를제조하였다.
[144]
[145] <제조예 13>
[146] CuS입자의함성 [147] 도데실아민 (Dodecylamine) 1 g이포함된 DEG용액 200 mL을섭씨 120도 이상으로가열한다음 10 mm이의티오아세트아미드 (thioacetamide)를포함하는 DEG용액 50 mL을적가한후, 5 mm이의 ^ᄋ 을포함하는 DEG용액 50 mL를적가하고,온도를유지하면서 3시간동안교반하여반웅시키고，형성된 입자를원심분리법으로정제하여 CuS나노입자를제조하였다.형성된입자를 분석한전자현미경 (SEM)사진및 XRD그래프를도 1및도 2에나타냈다.
[148]
[149] <제조예 14>
[150] CuS입자의합성
[151] 5 mm 의티오황산나트륨 (sodium thiosulfate)를포함하는수용액 100 mL에 50 mm이의시트르산 (citric acid)를포함하는수용액 100 mL을적가한후，섭씨 80도 이상으로가열한다음, 5 mm이의 1(1^03)2을포함하는수용액 50 mL을 적가하고，온도를유지하면서 3시간동안교반하여반웅시키고，형성된입자를 원심분리법으로정제하여 CuS나노입자를제조하였다.형성된입자를분석한 전자현미경 (SEM)사진및 XRD그래프를도 3및도 4에나타냈다.
[152]
[153] <제조예 15>
[154] CuS ¾자의합성
[155] 5 mm이의티오황산나트륨 (sodium thiosulfate)를포함하는 EG용액 100 mL에 50 mm이의시트르산 (citric acid)를포함하는 EG용액 100 mL을적가한후，섭씨 80도 이상으로가열한다음, 5 mm이의 Cu(N03)2을포함하는 EG용액 50 mL를적가한 후，은도를유지하면서 3시간동안교반하여반웅시키고,형성된입자를 원심분리법으로정제하여 CuS나노입자를제조하였다.
[156]
[157] <제조예 16>
[158] CuS입자의합성
[159] 5 mm이의티오요소 (thiourea)를포함하는 EG용액 100 mL를섭씨 80도
이상으로가열한다음, 5 mm이의 1(1^03)2을포함하는 EG용액 100 mL을적가한 후,온도를유지하면서 3시간동안교반하여반응시키고,형성된입자를 원심분리법으로정제하여 CuS나노입자를제조하였다.
[160]
[161] <제조예 17>
[162] CuS-ZnS입자의합성
[163] 도데실아민 (Dodecylamine) 1 g이포함된 DEG용액 200 mL를섭씨 120도
이상으로가열한다음 10 mn )l의티오아세트아미드 (thioacetamide)를포함하는 DEG용액 50 mL를적가한후, 5 mm이의 Cu(N03)2을포함하는 DEG용액 50 mL를적가하고,온도를유지하면서 3시간동안교반하여반응시키고,형성된 입자를원심분리법으로정제하여 CuS나노입자를제조하였다.얻어진 CuS나노 입자증 100 mg을 DEG용액 100 mL에재분산한다음, 10 mm 의 티오아세트아미드및 5 mmd의 ZnCl2를포함하는 DEG용액 100 mL를적가한 다음,섭씨 120도이상으로가열하고，온도를유지하며 3시간동안교반한다음, 원심분리법으로정제하여입자를얻었다.형성된입자를분석한
전자현미경 (SEM)사진및투과식전자현미경사진 (TEM)을도 5및도 6에 나타내었다
[164]
[165] <실시예 1>
[166] CuS-SnS-ZnS 3층코어-쉠나노입자의합성
[167] 제조예 13에의해 CuS코어입자를합성한다음，상은에서 10 mm이의
티오아세트아미드 (thioacetamide)를포함하는 EG용액을넣은다음에 5 mm이의 SnCI2를포함하는 EG용액을다시천천히적가한후，섭씨 125도까지온도를 올린후 3시간동안교반하여반웅시켰다.상기반웅으로코어-쉘구조의나노 입자를형성시킨후에，원심분리하여 CuS-SnS입자를얻고 DMSO에재분산한 다음，다시상온에서 lO mmol의티오아세트아미드 (thioacetamide)를포함하는 DEG용액을넣은다음에 6 mm이의 02를포함하는 DEG용액을다시천천히 적가한후，섭씨 130도까지은도를을린후 3시간동안교반하여반웅시키고, 형성된입자를원심분리법으로정제하여 3층코어-쉘구조의 CuS-SnS-ZnS나노 입자를제조하였다.
[168]
[169] <실시예 2>
[170] CuS-ZnS-SnS 3층코어-쉠나노입자의합성
[171] 제조예 13에의해 CuS코어입자를합성한다음,상온에서 10 mm이의
티오아세트아미드 (thioacetamide)를포함하는 DEG용액을넣은다음에섭
[172] 씨 130도까지온도를올리면서 6 mm이의 ZnCl2를포함하는 DEG용액을다 [173] 시천천히적가한후,섭씨 130도에서 3시간동안교반하여반웅시켰다.상기 반웅으로코어-쉘구조의나노입자를형성시킨후에，원심분리하여 CuS-ZnS 입자를얻고 EG에재분산한다음，다시상온에서 10 mm이의
티오아세트아미드 (thioacetamide)를포함하는 EG용액을넣은다음에 5 mm이의 SnCl2를포함하는 EG용액을다시천천히적가한후，섭씨 125도까지온도를 올린후 3시간동안교반하여반웅시키고，형성된입자를원심분리법으로 정제하여 3층코어-쉘구조의 CuS-ZnS-SnS나노입자를제조하였다.형성된 입자를분석한전자현미경 (SEM)사진및 XRD그래프와투과식전자현미경 사진 (TEM)을도 7내지도 10에나타내었다.
[174]
[175] <실시예 3>
[176] 박막의제조
[177] 실시예 19에의해합성된나노입자를알콜계용매로이루어진흔합용매에 분산하여잉크를제조한후，몰리브덴 (Mo)이코팅된유리기판 (glass substrate) 위에코팅하였다.상기코팅막을건조시킨후， Se이증착된유리기판과함께 가열하여 Se분위기가조성될수있도록한후섭씨 575도로 RTA(Rapid Thermal Annealing)하여 CZTSSe계박막을제조하였다.얻어진박막을분석한
전자현미경 (SEM)사진을도 11에나타내었다.
[178]
[179] 상기의결과로부터알수있는바와같이본발명에서서술한 3층코어-쉘
구조의입자를전구체로사용하여 CZTS태양전지를만들수있으며,이를 전구체로사용하여박막을제조하는경우，수백나노미터의미시영역에서 CZTS에필수적인원소들이모두존재하며，이원소들이원하는비율로존재하기 때문에짧은 RTA공정에서도양질의막질을제공할수있을뿐아니라，박막의 전체적인조성균일성을확보할수있어전자의이동을용이하게함으로써 전체적인광전환효율이향상된태양전지를만들수있다.
[180]
[181] 본발명이속한분야에서통상의지식을가진자라면상기내용을바탕으로본 발명의범주내에서다양한응용및변형을행하는것이가능할것이다.
[182]
산업상이용가능성
[183] 이상에서설명한바와같이，본발명에따라구리 (Cu)함유칼코게나이드를 포함하는코어 (core)와,주석 (Sn)함유칼코게나이드 (i)주석 (Sn)함유
칼코게나이드를포함하는제 1쉘 (shell)및아연 (Zn)함유칼코게나이드를 포함하는제 2쉘 (shell);또는 (ii)아연 (Zn)함유칼코게나이드를포함하는제 1 쉘 (shell)및주석 (Sn)함유칼코게나이드를포함하는제 2쉘 (shell);로이루어진 3층코어-쉘구조의나노입자를사용하여광흡수충을제조하는경우,공정 비용을낮출수있고,안전한공정이가능하여생선성을높일수있는효과가 있다.
[184] 또한，상기 3층코어-쉘구조의나노입자는산화에안정하고,반웅성이우수한 바，이를사용하여박막을제조하는경우,양질의막질을제공할수있을뿐 아니라，한입자내에 Cu, Sn, Zn, S또는 Se를모두포함하고있어박막의 전체적인조성균일성을확보할수있는바，결과적으로본발명에따른 태양전지의광전효율이향상되는효과가있다.
[185]

Claims

청구범위
태양전지의광흡수층을형성하는 3층코어-쉘구조의나노 입자로서，구리 (Cu)함유칼코게나이드를포함하는코어 (core)와,
(i)주석 (Sn)함유칼코게나이드를포함하는제 1쉘 (shell)및 아연 (Zn)함유칼코게나이드를포함하는제 2쉘 (shell);또는
(ii)아연 (Zn)함유칼코게나이드를포함하는제 1쉘 (shell)및 주석 (Sn)함유칼코게나이드를포함하는제 2쉘 (shell);
로이루어진것을특징으로하는 3층코어-쉘구조의나노입자. 제 1항에있어서，상기코어의입경은 20나노미터내지 200 나노미터인것을특징으로하는 3층코어-쉘구조의나노입자. 제 1항에있어서，상기제 1쉘또는제 2쉘에포함되는아연 (Zn) 함유칼코게나이드의중량은상기코어에포함되는구리 (Cu)함유 칼코게나이드 100중량부대비 35내지 100중량부인것을 특징으로하는 3층코어-쉘구조의나노입자.
제 1항에있어서，상기제 1쉘또는제 2쉘에포함되는주석 (Sn) 함유칼코게나이드의증량은상기코어에포함되는구리 (Cu)함유 칼코게나이드 100중량부대비 40내지 65중량부인것을특징으로 하는 3층코어-쉘구조의나노입자.
제 1항에있어서,구리 (Cu)함유칼코게나이드는 CuS, Cux S(1.7<x<2.0), CuSe,및 CuySe(1.7≤y≤2.0)로이루어지는
군으로부터선택되는하나이상인것을특징으로하는 3층 코어-쉘구조의나노입자.
제 1항에있어서，주석 (Sn)함유칼코게나이드는 SnS,및 /또는 SnSe인것을특징으로하는 3층코어-쉘구조의나노입자.
제 1항에있어서,아연 (Zn)함유칼코게나이드는 ZnS,및 /또는 ZnSe인것을특징으로하는 3층코어-쉘구조의나노입자.
제 1항에따른 3층코어-쉘구조의나노입자를합성하는 방법으로서,
(i)황 (S),또는셀레늄 (Se),또는황 (S)및셀레늄 (Se)을포함하는 화합물로이루어진군에서선텍되는 1종이상의 VI족소스를 포함하는제 1용액을준비하는과정;
(ii)구리 (Cu)염을포함하는제 2용액과주석 (Sn)염을포함하는제 3용액및아연 (Zn)염을포함하는제 4용액을준비하는과정;
(iii)상기제 1용액과제 2용액을흔합하여혼합물을제조하고， 반웅시켜구리 (Cu)함유칼코게나이드코어입자를합성하는 과정;
(iv)상기과정 (iii)의코어입자를포함하는생성물에상기제 3 용액이나제 4용액을혼합하여제 1쉘을형성하는과정 ;
(V)상기과정 (iv)의제 1쉘이형성된코어-쉘구조의나노입자를 포함하는생성물에상기과정 (iv)에포함되지않은제 4용액이나 제 3용액을흔합하여제 2쉘을형성하여 3층코어-쉘구조의나노 입자를합성한후，정제하는과정；
을포함하는것을특징으로하는 3층코어-쉘구조의나노입자 합성방법ᅳ
제 8항에있어서，상기제 1용액내지제 4용액의용매는물, 메탄을 (methanol),에탄올 (ethanol),글리콜류용매,
오레일아민 (oleylamine)，디메틸설폭사이드 (dimethyl sulfoxide),및 디메틸포름아마이드 (dimethyl formamide)로이투어진군에서 선택되는하나이상인것을특징으로하는 3층코어-쉘구조의 나노입자합성방법.
제 9항에있어서，상기글리콜류용매는
에틸렌글리콜 (ethyleneglycol),디에틸렌글리콜 (diethylene glycol), NMP,디에틸렌글리콜모노에틸에테르 (diethylene glycol mono ethyl ether: DEGMEE)및트리에틸렌글리콜 (triethylene glycol)으로 이루어진군에서선택되는어느하나인것을특징으로하는 3층 코어-쉘구조의나노입자합성방법.
제 8항에있어서，상기염은염화물 (chloride),질산염 (nitrate), 아질산염 (nitrite),황산염 (sulfate),아세트산염 (acetate),
아황산염 (sulfite),아세틸아세토네이트염 (acetylacetoante)및 수산화물 (hydroxide)로이루어진군에서선텍되는하나이상의 형태인것을특징으로하는 3층코어-쉘구조의나노입자 합성방법.
제 8항에있어서，상기 VI족소스는 Se, Na2Se, K2Se, Ca2Se, (CH3)2 Se, Se02, SeCl4, H2Se03, Na2S, K2S, Ca2S, (CH3)2S, H2S04, S, Na2S203, NH2S03H및이들의수화물로이루어진군에서선택되는하나 이상인것을특징으로하는 3층코어ᅳ쉘구조의나노입자 합성방법.
제 8항에있어서，상기 VI족소스는티오요소 (thiourea), 티오아세트아미드 (thioacetamide),및
샐레노유레아 (selenourea)으로이루어진군에서선택되는하나 이상인것을톡징으로하는 3층코어-쉘구조의나노입자 합성방법.
제 8항에있어서，상기과정 (iii)의흔합물에서 VI족소스는 구리 (Cu)염 1몰에대해 0.5내지 4몰로포함되어있는것을 특징으로하는 3층코어-쉘구조의나노입자합성방법 . 제 8항에있어서，상기제 3용액중의주석 (Sn)염의농도는, 주석 (Sn)/구리 (Cu)의몰비가 0.5내지 3이되는범위에서정해지는 것을특징으로하는 3층코어-쉘구조의나노입자합성방법 . 제 8항에있어서,상기제 4용액중의아연 (Zn)염의농도는, 아연 (Zn)/구리 (Cu)의몰비가 0.6내지 3이되는범위에서정해지는 것을특징으로하는 3층코어 -쉘구조의나노입자합성방법 . 제 8항에있어서，상기과정 (iv)의코어입자를포함하는생성물에 제 1쉘을형성시또는과정 (V)의제 1쉘이형성된코어-쉘구조의 나노입자를포함하는생성물에제 2쉘을형성시추가로 VI족 소스를첨가하는것을특징으로하는 3층코어-쉘구조의나노 입자합성방법.
제 8항에따른 3층코어-쉘구조의나노입자에기반한
광흡수층을포함하는박막을제조하는방법으로서 ,
(i) 3층코어-쉘구조의나노입자를용매에분산하여잉크를 제조하는과정;
(ii)전극이형성된기재상에상기잉크를코팅하는과정;및 (Hi)상기전극이형성된기재상에코팅된잉크를건조한후 열처리하는과정;
을포함하는것을특징으로하는박막의제조방법 .
제 18항에있어서,상기과정 (i)의용매는알칸계 (alkanes), 알켄계 (alkenes),알킨계 (alkynes),방향족화합물계 (aromatics), 케톤계 (ketons),니트릴계 (nitriles),에테르계 (ethers),
에스테르계 (esters),유기할로겐화물계 (organic halides),
알코올계 (alcohols),아민계 (amines),티올계 (thiols),카르복실 산겨 carboxylic acids),수소화인계 (phosphines),
인산염계 (phosphates),황산화물계 (sulfoxides),및아미드계 (amides) 이루어진군으로부터선택된하나이상의유기용매인것을 특징으로하는박막의제조방법.
제 18항에있어서,상기과정 (i)의잉크는첨가제를더포함하여 제조되는것을특징으로하는박막의제조방법 .
제 20항에있어서,상기첨가제는
폴리비닐피로리돈 (Poly vinylpyrrolidone: PVP),
폴리비닐알코올 (Polyvinylalcohol),안티테라 204(Anti-terra 204), 안티테라 205(Anti-terra 205),에틸셀를로오스 (ethyl cellulose),및 디스퍼스 BYKl lO(DispersBYKllO)으로이루어진군에서선택되는 어느하나이상인것을특징으로하는박막의제조방법 .
제 18항에있어서,상기과정 (iii)의열처리는섭씨 400내지 900도 범위의온도에서수행되는것을특징으로하는박막의제조방법. [청구항 23] 제 18항내지제 22항중어느하나에따른방법으로제조된것을 특징으로하는박막,
[청구항 24] 제 23항에따른박막을사용하여제조되는박막태양전지 .
PCT/KR2014/007091 2013-08-01 2014-08-01 태양전지 광흡수층 제조용 3층코어-쉘 나노 입자 및 이의 제조 방법 WO2015016650A1 (ko)

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