TWI614216B - Method of manufacturing ITO particles - Google Patents
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- TWI614216B TWI614216B TW102143768A TW102143768A TWI614216B TW I614216 B TWI614216 B TW I614216B TW 102143768 A TW102143768 A TW 102143768A TW 102143768 A TW102143768 A TW 102143768A TW I614216 B TWI614216 B TW I614216B
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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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- 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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Description
本發明有關一種適用於有必要將太陽能電池、觸控面板及液晶面板等不同種類材料電性接合之電子裝置之ITO粒子。本說明書中，ITO係指銦錫氧化物(Indium Tin Oxide)。 The present invention relates to an ITO particle suitable for use in an electronic device in which a different type of material such as a solar cell, a touch panel, or a liquid crystal panel is electrically bonded. In the present specification, ITO means indium tin oxide (Indium Tin Oxide).
以往，揭示有利用濕式塗佈法在光電轉換層上形成由透明導電膜與導電性反射膜構成之複合膜作為背面電極之超直型(super straight)薄膜太陽能電池(例如，參考專利文獻1)。作為包含於用以形成該透明導電膜之組成物的導電性氧化物微粒之一，已揭示有ITO粒子。該ITO粒子係藉由如下製造，即在銦化合物與錫化合物之混合水溶液中混合鹼水溶液，以生成銦與錫之共沉澱氫氧化物，並水洗該沉澱物，丟棄上述沉澱物之上澄液而製備分散有銦錫氫氧化物粒子之漿料，並對該漿料進行乾燥之後，對經乾燥之銦錫氫氧化物進行燒成。 In the past, a super straight thin film solar cell in which a composite film composed of a transparent conductive film and a conductive reflective film is formed as a back electrode on a photoelectric conversion layer by a wet coating method has been disclosed (for example, Patent Document 1) ). As one of the conductive oxide fine particles contained in the composition for forming the transparent conductive film, ITO particles have been disclosed. The ITO particles are produced by mixing an aqueous alkali solution in a mixed aqueous solution of an indium compound and a tin compound to form a coprecipitated hydroxide of indium and tin, and washing the precipitate with water, discarding the above precipitate. On the other hand, a slurry in which indium tin hydroxide particles are dispersed is prepared, and after drying the slurry, the dried indium tin hydroxide is fired.
考慮上述太陽能電池之發電效率時，期望背面電極之主成分的ITO粒子之功函數儘可能低。以開爾文 法(Kelvin method)對由上述以往方法所製造之ITO粒子之功函數進行測定時，其功函數為5.33eV，另一方面以開爾文法對由非晶矽或多晶矽構成之光電轉換層、即發電層之功函數進行測定時，其功函數為4.8eV，與ITO粒子之功函數之差為0.53eV。所謂開爾文法係測定試料與測定用電極之間的接觸電位差，且以參考電極校正已知功函數之金屬，藉此測定目標試料之功函數的方法。參考電極通常使用功函數已知、未形成自然氧化膜，且表面穩定之金。 In consideration of the power generation efficiency of the above solar cell, it is desirable that the work function of the ITO particles as the main component of the back electrode is as low as possible. Kelvin When the Kelvin method measures the work function of the ITO particles produced by the above conventional method, the work function is 5.33 eV, and on the other hand, the photoelectric conversion layer composed of amorphous germanium or polycrystalline germanium is generated by the Kelvin method, that is, power generation. When the work function of the layer was measured, the work function was 4.8 eV, and the difference from the work function of the ITO particles was 0.53 eV. The Kelvin method is a method of measuring the work potential of a target sample by measuring the contact potential difference between the sample and the electrode for measurement, and correcting the metal of the known work function with the reference electrode. The reference electrode usually uses a gold whose work function is known, a natural oxide film is not formed, and the surface is stable.
專利文獻2中已記載通常由ITO形成之透明電極的功函數為4.5~5.1eV，其實施例中記載膜厚為150nm之ITO設置在單面之附有ITO之玻璃基板。設置於該玻璃基板上之ITO透明導電膜通常係以濺射法形成，且其功函數以紫外光電子分光法(UPS)測定，與Si的功函數4.05eV之差為0.45~1.05eV，因此以開爾文法進行測定時，推測以濺射法形成之ITO透明導電膜之功函數達到5.25~5.95eV。 Patent Document 2 discloses that a work function of a transparent electrode formed of ITO is generally 4.5 to 5.1 eV. In the examples, ITO having a film thickness of 150 nm is provided on a single-sided ITO-attached glass substrate. The ITO transparent conductive film disposed on the glass substrate is usually formed by a sputtering method, and its work function is measured by ultraviolet photoelectron spectroscopy (UPS), and the difference from the work function of Si of 4.05 eV is 0.45 to 1.05 eV, so When measured by the Kelvin method, it is presumed that the work function of the ITO transparent conductive film formed by the sputtering method is 5.25 to 5.95 eV.
[專利文獻1]：日本特開2009-088489號公報(摘要、段落[0042]) [Patent Document 1]: JP-A-2009-088489 (Summary, paragraph [0042])
[專利文獻2]：日本特開2006-351721號公報(段落[0024]、[0034]) [Patent Document 2]: JP-A-2006-351721 (paragraphs [0024], [0034])
根據前述以往之方法，對經乾燥之銦錫氫氧化物進行燒成而製造之ITO粒子之功函數範圍較高而為超過5.3eV且5.4eV以下(開爾文法測定值)，因此容易在太陽能電池之背面電極與發電層之間產生功函數之差，因該差而在ITO粒子之界面形成能障，且因該能障而難以提高太陽能電池之發電效率。具體而言，當電性接合不同種類材料時，若兩種材料間之功函數差達到0.5eV以上，則會在接合界面形成位障(potential barrier)(稱為肖特基位障(schottky barrier))。若形成該位障，則在電子傳播時成為屏障，使界面成為高電阻層。將ITO粒子用在太陽能電池之背面電極時，ITO與Si之界面成為高電阻，而有導致太陽能電池之發電效率下降之問題點。 According to the above-described conventional method, the ITO particles produced by firing the dried indium tin hydroxide have a high work function range of more than 5.3 eV and 5.4 eV or less (Kelvin method), and thus are easily used in solar cells. A difference in work function occurs between the back electrode and the power generation layer, and an energy barrier is formed at the interface of the ITO particles due to the difference, and it is difficult to increase the power generation efficiency of the solar cell due to the energy barrier. Specifically, when electrically bonding different kinds of materials, if the work function difference between the two materials reaches 0.5 eV or more, a potential barrier is formed at the joint interface (referred to as a Schottky barrier). )). When this barrier is formed, it becomes a barrier during electron propagation, and the interface becomes a high resistance layer. When ITO particles are used for the back electrode of a solar cell, the interface between ITO and Si becomes high resistance, and there is a problem that the power generation efficiency of the solar cell is lowered.
本發明之目的係提供一種ITO粒子，其在將ITO粒子使用於太陽能電池之背面電極時，可減少ITO粒子與發電層之界面的能障，藉此提高太陽能電池之發電效率。且本發明之另一目的係提供一種太陽能電池之製造方法，其係藉由具有由包含該ITO粒子之ITO導電膜塗料形成之透明導電膜，可降低發電層與以ITO粒子為主成分之背面電極間之功函數差而提高太陽能電池之發電效率。 An object of the present invention is to provide an ITO particle which can reduce the energy barrier of the interface between the ITO particles and the power generation layer when the ITO particles are used for the back electrode of the solar cell, thereby improving the power generation efficiency of the solar cell. Another object of the present invention is to provide a method for producing a solar cell by reducing a power generation layer and a back surface mainly composed of ITO particles by having a transparent conductive film formed of an ITO conductive film coating containing the ITO particles. The difference in work function between the electrodes improves the power generation efficiency of the solar cell.
本發明之第1觀點係一種ITO粒子，其特徵係於以金為基準而以開爾文法反覆進行測定時，具有4.8~5.3eV範圍之功函數者。 The first aspect of the present invention is an ITO particle characterized by having a work function in the range of 4.8 to 5.3 eV when measured by the Kelvin method on the basis of gold.
另本發明之第2觀點係一種ITO導電膜塗料，其特徵係包含第1觀點之ITO粒子者。 According to a second aspect of the invention, there is provided an ITO conductive film coating characterized by comprising the ITO particles of the first aspect.
且本發明之第3觀點係一種形成透明導電膜之方法，其係利用以第2觀點之方法所製造之ITO導電膜塗料者。 Further, a third aspect of the present invention is a method for forming a transparent conductive film, which is the ITO conductive film coating produced by the method of the second aspect.
另外，本發明之第4觀點係一種太陽能電池之製造方法，該太陽能電池具有以第3觀點之方法形成之透明導電膜。 Further, a fourth aspect of the present invention provides a method of producing a solar cell comprising the transparent conductive film formed by the method of the third aspect.
本發明之第1觀點之ITO粒子以開爾文法進行測定時，具有比以往的5.33eV低之4.8~5.3eV範圍的功函數，因此用在太陽能電池之背面電極時，能夠減少ITO粒子與發電層之界面的能障，藉此提高太陽能電池之發電效率。 When the ITO particles of the first aspect of the present invention have a work function in the range of 4.8 to 5.3 eV lower than the conventional 5.33 eV when measured by the Kelvin method, the ITO particles and the power generation layer can be reduced when used in the back electrode of a solar cell. The energy barrier of the interface, thereby improving the power generation efficiency of the solar cell.
本發明第4觀點之太陽能電池之製造方法藉由具有由包含ITO粒子之ITO導電膜塗料形成之透明導電膜，而可降低發電層與以ITO粒子為主成分之背面電極間之功函數差以提高太陽能電池之發電效率。 According to a fourth aspect of the present invention, in a method for producing a solar cell, a transparent conductive film formed of an ITO conductive film coating containing ITO particles can reduce a work function difference between a power generation layer and a back electrode having ITO particles as a main component. Improve the power generation efficiency of solar cells.
圖1係表示實施例1~6及比較例1之各ITO 粒子之功函數與由將各ITO粒子用在背面電極而製作之薄膜太陽能電池單元所算出之曲線因子之關係圖。 1 shows the respective ITOs of Examples 1 to 6 and Comparative Example 1. A graph showing the relationship between the work function of the particles and the curve factor calculated from the thin film solar cells produced by using the respective ITO particles on the back electrode.
接著，對用以實施本發明之形態進行說明。本發明之ITO粒子以開爾文法進行測定時，具有比以往之5.33eV低的4.8~5.3eV範圍之功函數。功函數4.8eV為以現有技術可達到的最小值。若超過5.3eV，則將ITO粒子用在太陽能電池之背面電極時，容易於ITO粒子與發電層之界面形成能障，因此有無法提高太陽能電池之發電效率之不良情況。在ITO與Si之界面，由於ITO之功函數大於Si之功函數，因此為了減小ITO與Si之功函數差，需要降低ITO之功函數。作為降低該ITO功函數之方法有如下方法：第一，提高ITO載子濃度之方法；第二，對ITO粒子表面進行改質之方法。基於該等想法，本發明人等發現了以下所示之降低功函數之四種製造方法。第1製造方法係在剛生成的粒子內，對不均勻地混合有In與Sn之狀態的氫氧化物照射紫外線，以促進In與Sn均勻地固溶，藉此增加ITO粒子之載子濃度，並且抑制SnO2朝ITO表面偏析，藉此可降低ITO粒子之功函數。第2製造方法係使霧狀氫氧化物之漿料流入到加熱之爐內，並急速地進行加熱．熱分解，藉此抑制SnO2朝ITO表面偏析，並且藉由在還原氛圍中進行加熱，以增加ITO粒子之載子濃度，藉此可降低ITO粒子之功函數。第3製造方法係在 還原性溶劑中利用雷射賦予較大能量，以對氫氧化物之粒子進行急速加熱．熱分解，以抑制SnO2朝ITO表面偏析，並且增加ITO粒子之載子濃度，藉此可降低ITO粒子之功函數。第4製造方法係藉由在還原氛圍中之加熱，而增加ITO粒子之載子濃度，藉此可降低ITO粒子之功函數。 Next, a mode for carrying out the invention will be described. When the ITO particles of the present invention are measured by the Kelvin method, they have a work function in the range of 4.8 to 5.3 eV which is lower than the conventional 5.33 eV. The work function 4.8 eV is the minimum that can be achieved with the prior art. When it exceeds 5.3 eV, when ITO particles are used for the back electrode of a solar cell, it is easy to form an energy barrier at the interface between the ITO particle and the power generation layer, and there is a problem that the power generation efficiency of the solar cell cannot be improved. At the interface between ITO and Si, since the work function of ITO is larger than the work function of Si, in order to reduce the work function difference between ITO and Si, it is necessary to reduce the work function of ITO. As a method for lowering the work function of the ITO, there are the following methods: first, a method of increasing the concentration of the ITO carrier; and second, a method of modifying the surface of the ITO particle. Based on these ideas, the inventors have found four manufacturing methods for reducing the work function shown below. In the first production method, the hydroxide in a state in which In and Sn are unevenly mixed is irradiated with ultraviolet rays in the newly formed particles to promote uniform solid solution of In and Sn, thereby increasing the carrier concentration of the ITO particles. Further, segregation of SnO 2 to the surface of the ITO is suppressed, whereby the work function of the ITO particles can be lowered. In the second manufacturing method, the slurry of the mist hydroxide is poured into the heating furnace, and the heating is rapidly performed. Thermal decomposition, thereby suppressing the segregation of SnO 2 toward the ITO surface, and heating in a reducing atmosphere to increase the carrier concentration of the ITO particles, thereby reducing the work function of the ITO particles. The third manufacturing method uses a laser to impart a large amount of energy in a reducing solvent to rapidly heat the particles of the hydroxide. Thermal decomposition to suppress segregation of SnO 2 toward the ITO surface and increase the carrier concentration of the ITO particles, whereby the work function of the ITO particles can be lowered. In the fourth manufacturing method, the carrier concentration of the ITO particles is increased by heating in a reducing atmosphere, whereby the work function of the ITO particles can be lowered.
以下對用於降低該ITO粒子之功函數的ITO粒子之具體製造方法加以敍述。但本發明之ITO粒子之製造方法並不限於該四種方法。 A specific manufacturing method of ITO particles for reducing the work function of the ITO particles will be described below. However, the method of producing the ITO particles of the present invention is not limited to the four methods.
(1)第1製造方法 (1) First manufacturing method
溶液中，使3價銦化合物與2價或4價錫化合物在鹼存在下沉澱，且生成銦與錫的共沉澱氫氧化物。此時，將溶液之pH調整為4.0~9.3，較好調整為pH6.0~8.0，並將溶液溫度調整為5℃以上，較好將溶液溫度調整為10℃~80℃，藉此可使銦錫之共沉澱氫氧化物沉澱。將反應時之液性調整為pH4.0~9.3時，較好例如利用三氯化銦(InCl3)與氯化亞錫(SnCl2‧2H2O)之混合水溶液，並在水中同時滴入該混合水溶液與鹼水溶液，而調整至上述pH範圍。或者，在鹼水溶液中滴入上述混合水溶液。鹼水溶液係使用氨(NH3)水、碳酸氫銨(NH4HCO3)水等。 In the solution, a trivalent indium compound and a divalent or tetravalent tin compound are precipitated in the presence of a base, and a coprecipitated hydroxide of indium and tin is formed. At this time, the pH of the solution is adjusted to 4.0 to 9.3, preferably adjusted to pH 6.0 to 8.0, and the solution temperature is adjusted to 5 ° C or higher, preferably the solution temperature is adjusted to 10 ° C to 80 ° C, thereby The coprecipitated hydroxide precipitated in indium tin. When the liquidity at the time of the reaction is adjusted to pH 4.0 to 9.3, it is preferred to use, for example, a mixed aqueous solution of indium trichloride (InCl 3 ) and stannous chloride (SnCl 2 ‧2H 2 O), and simultaneously drip in water. The mixed aqueous solution and the aqueous alkali solution were adjusted to the above pH range. Alternatively, the above mixed aqueous solution is dropped into an aqueous alkali solution. As the aqueous alkali solution, ammonia (NH 3 ) water, ammonium hydrogencarbonate (NH 4 HCO 3 ) water or the like is used.
生成上述共沉澱銦錫氫氧化物後，用純水清洗該沉澱物，並將其清洗至上澄液之電阻率達到 5000Ω‧cm以上，較好達到50000Ω‧cm以上為止。若上澄液之電阻率低於5000Ω‧cm，則氯等雜質未被充分去除，而無法獲得高純度之銦錫氧化物粉末。丟棄電阻率達到5000Ω‧cm以上的上述沉澱物之上澄液，作成高黏度之漿料狀，邊攪拌該漿料邊以1~50小時之範圍照射126~365nm範圍之紫外線。若紫外線之波長未達下限值，則無法使用泛用之紫外線照射裝置，若超過上限值，則上述沉澱物缺乏紫外線吸收，而無法獲得照射紫外線之效果。其照射時間若未達下限值，則上述沉澱物缺乏紫外線吸收，無法獲得照射紫外線之效果，即使以超過其上限值之時間照射紫外線仍無法獲得其效果。 After the above-mentioned coprecipitated indium tin hydroxide is formed, the precipitate is washed with pure water and washed until the resistivity of the supernatant liquid reaches 5000 Ω ‧ cm or more, preferably up to 50,000 Ω ‧ cm or more If the resistivity of the supernatant liquid is less than 5000 Ω ‧ cm, impurities such as chlorine are not sufficiently removed, and high-purity indium tin oxide powder cannot be obtained. The above-mentioned precipitate having a specific resistance of 5000 Ω ‧ cm or more is discarded to form a slurry having a high viscosity, and the ultraviolet ray in the range of 126 to 365 nm is irradiated for 1 to 50 hours while stirring the slurry. When the wavelength of the ultraviolet ray does not reach the lower limit value, the ultraviolet ray irradiation apparatus which is used in general can not be used, and if it exceeds the upper limit value, the above-mentioned precipitate lacks ultraviolet ray absorption, and the effect of irradiating ultraviolet rays cannot be obtained. If the irradiation time is less than the lower limit, the precipitate lacks ultraviolet absorption, and the effect of irradiating ultraviolet rays cannot be obtained, and the effect cannot be obtained even if the ultraviolet rays are irradiated for a time exceeding the upper limit.
照射紫外線後，在大氣中，較好在氮或氬等惰性氣體氛圍下，以100~200℃之範圍對漿料狀銦錫氫氧化物進行2~24小時之乾燥，之後在大氣中以250~800℃之範圍進行0.5~6小時之燒成。利用錘式粉碎機或球磨機等對藉由該燒成所形成之聚集體進行粉碎並使之鬆散，獲得ITO粒子。將該ITO粒子加入到使50~95質量份之無水乙醇與5~50質量份之蒸餾水混合的溶液中，使其含浸後，加入到玻璃皿中，並在氮氣氛圍下以200~400℃之範圍加熱0.5~5小時，即獲得本發明之ITO粒子。該ITO粒子之功函數可藉由改變上述紫外線之照射時間加以控制。 After the ultraviolet ray is irradiated, the slurry-like indium tin hydroxide is dried in the atmosphere at a temperature of 100 to 200 ° C for 2 to 24 hours in an atmosphere of an inert gas such as nitrogen or argon, and then 250 in the atmosphere. The firing is carried out in the range of ~800 ° C for 0.5 to 6 hours. The aggregate formed by the firing is pulverized and loosened by a hammer mill or a ball mill or the like to obtain ITO particles. The ITO particles are added to a solution in which 50 to 95 parts by mass of absolute ethanol is mixed with 5 to 50 parts by mass of distilled water, impregnated, and then added to a glass dish at 200 to 400 ° C under a nitrogen atmosphere. The ITO particles of the present invention are obtained by heating in the range of 0.5 to 5 hours. The work function of the ITO particles can be controlled by changing the irradiation time of the above ultraviolet rays.
(2)第2製造方法 (2) Second manufacturing method
丟棄以第1製造方法所得之銦錫共沉澱氫氧化物的沉 澱物之上澄液獲得漿料狀之銦錫氫氧化物後，在使載氣的N2氣體流通至於管的長邊方向垂直配置且加熱到250~800℃之範圍之管狀爐內部之狀態下，利用40kHz~2MHz之超音波使漿料狀之銦錫氫氧化物氣化，對流通之N2氣體進行噴霧。超音波之頻率若未達下限值，則經霧化之包含銦錫氫氧化物之液滴較大，且液滴中之銦錫氫氧化物含量較多，因而有在進行熱分解時，ITO燒結而導致粗大化之不良情況，若超過上限值，則有霧化效率變差之不良情況。因此銦錫氫氧化物在管狀爐內熱分解，且自管狀爐之排出口獲得本發明之ITO粒子。該ITO粒子之功函數可藉由改變上述氣體之流速與爐內溫度加以控制。 Discarding the precipitate of the indium tin coprecipitated hydroxide obtained by the first production method to obtain a slurry-like indium tin hydroxide, and then flowing the carrier gas N 2 gas to the longitudinal direction of the tube. In the state in which the inside of the tubular furnace in the range of 250 to 800 ° C is placed and heated, the slurry-like indium tin hydroxide is vaporized by ultrasonic waves of 40 kHz to 2 MHz, and the circulating N 2 gas is sprayed. If the frequency of the ultrasonic wave does not reach the lower limit value, the droplets containing the indium tin hydroxide which are atomized are large, and the content of the indium tin hydroxide in the droplet is large, so that when thermal decomposition is performed, When the ITO is sintered and the coarsening is caused, if the ITO is exceeded, the atomization efficiency is deteriorated. Therefore, the indium tin hydroxide is thermally decomposed in the tubular furnace, and the ITO particles of the present invention are obtained from the discharge port of the tubular furnace. The work function of the ITO particles can be controlled by varying the flow rate of the above gas and the temperature in the furnace.
(3)第3製造方法 (3) Third manufacturing method
丟棄以第1製造方法所得之銦錫共沉澱氫氧化物的沉澱物之上澄液獲得漿料狀之銦錫氫氧化物後，在大氣中，較好在氮或氬等惰性氣體氛圍下，以100~200℃之範圍對該銦錫氫氧化物進行2~24小時之乾燥，獲得銦錫氫氧化物粉末。對該銦錫氫氧化物粉末之分散溶液照射雷射光。該方法中可使用之雷射種類只要是可產生高強度脈衝光之雷射即可，例如可利用Nd：YAG雷射、準分子雷射、Ti藍寶石雷射，較好使用Nd：YAG雷射。雷射光之照射強度只要是溶液中之銦錫氫氧化物受到雷射光照射後可燒蝕之充分強度即可，作為每1脈衝之強度若為10mJ(10mJ/脈衝)以上即已足夠，較好為50mJ/脈衝~500mJ/脈衝。 且雖然沒有限定雷射光之脈衝寬度，但較好為1nm~20ns，作為峰值(峰值功率)較好為0.5~500MW。此外，雖沒有限定雷射之振盪頻率(脈衝週期)，但較好為10~60Hz，平均功率較好為0.1~30W。 Discarding the precipitate of the indium tin coprecipitated hydroxide obtained by the first production method to obtain a slurry of indium tin hydroxide, and then in an atmosphere, preferably under an inert gas atmosphere such as nitrogen or argon, The indium tin hydroxide is dried in a range of 100 to 200 ° C for 2 to 24 hours to obtain an indium tin hydroxide powder. The dispersion solution of the indium tin hydroxide powder is irradiated with laser light. The laser type that can be used in the method can be any laser that can generate high-intensity pulsed light, for example, Nd:YAG laser, excimer laser, Ti sapphire laser, and Nd:YAG laser can be preferably used. . The irradiation intensity of the laser light is sufficient as long as the indium tin hydroxide in the solution is ablated by the laser light, and it is sufficient if the intensity per pulse is 10 mJ (10 mJ/pulse) or more. It is 50mJ/pulse ~500mJ/pulse. Although the pulse width of the laser light is not limited, it is preferably 1 nm to 20 ns, and the peak value (peak power) is preferably 0.5 to 500 MW. Further, although the oscillation frequency (pulse period) of the laser is not limited, it is preferably 10 to 60 Hz, and the average power is preferably 0.1 to 30 W.
在該方法中作為溶液之溶劑可使用水或醇或己烷等有機溶劑，對於該溶劑並無任何限制。較好相對於欲照射之雷射光之波長不具有強的光吸收之液體。例如，當使用波長為266~1064nm之Nd：YAG雷射光時，較好為去離子水、乙醇、甲醇、丁醇、異丙醇、丙醇。且，可在溶液中添加各種界面活性劑或金屬鹽、酸、鹼等物質作為添加劑，只要在溶液中可完全溶解，則其物質不受限制。與溶液同樣般，尤其較好使用對於欲照射之雷射光波長不具有強的光吸收之物質作為添加劑。例如，當使用波長為266~1064nm之Nd：YAG雷射光時，較好使用兩性離子界面活性劑、或陽離子性界面活性劑、非離子性界面活性劑等添加劑。 As the solvent of the solution in the method, water or an organic solvent such as an alcohol or hexane can be used, and there is no limitation on the solvent. A liquid which does not have a strong light absorption with respect to the wavelength of the laser light to be irradiated. For example, when Nd:YAG laser light having a wavelength of 266 to 1064 nm is used, it is preferably deionized water, ethanol, methanol, butanol, isopropanol or propanol. Further, various surfactants or metal salts, acids, bases and the like may be added to the solution as an additive, and the substance is not limited as long as it is completely soluble in the solution. As with the solution, it is particularly preferable to use, as an additive, a substance which does not have strong light absorption for the wavelength of the laser light to be irradiated. For example, when Nd:YAG laser light having a wavelength of 266 to 1064 nm is used, an additive such as a zwitterionic surfactant, a cationic surfactant, or a nonionic surfactant is preferably used.
使用去離子水作為溶液之溶劑時，雷射光波長並無特別限定，但較好為266~1064nm。當使用有機溶劑或界面活性劑時，較好為對於有機溶劑或界面活性劑不具有強吸收之波長，更好為355~1064nm。例如為去離子水、或乙醇、甲醇、丁醇、異丙醇、丙醇等醇時，可利用具有奈秒脈衝寬度之Nd：YAG雷射之基本波(波長：1064nm)、二次諧波(波長：532nm)、三次諧波(波長：355nm)、四次諧波(波長：266nm)等。 When deionized water is used as the solvent of the solution, the wavelength of the laser light is not particularly limited, but is preferably 266 to 1064 nm. When an organic solvent or a surfactant is used, it is preferably a wavelength which does not have a strong absorption for an organic solvent or a surfactant, and more preferably 355 to 1064 nm. For example, when deionized water or alcohol such as ethanol, methanol, butanol, isopropanol or propanol, a fundamental wave (wavelength: 1064 nm) having a nanosecond pulse width and a second harmonic can be used. (wavelength: 532 nm), third harmonic (wavelength: 355 nm), fourth harmonic (wavelength: 266 nm), and the like.
且較好透過聚光透鏡照射雷射光，但當雷射光強度足夠強時，亦可不使用聚光透鏡。所使用之聚光透鏡之焦距較好為50cm~3cm，更好為10cm~5cm。且，雷射光之聚光點只要存在於液體表面附近即可，最好位於液體中。分散於溶液中之ITO粒子濃度較好為10g/L以下，更好為0.02g/L以下，最好為0.005g/L以上且0.01g/L以下。 It is preferable to irradiate the laser light through the collecting lens, but when the intensity of the laser light is sufficiently strong, the collecting lens may not be used. The focal length of the collecting lens used is preferably from 50 cm to 3 cm, more preferably from 10 cm to 5 cm. Moreover, the spotlight of the laser light may be located in the vicinity of the surface of the liquid, preferably in a liquid. The concentration of the ITO particles dispersed in the solution is preferably 10 g/L or less, more preferably 0.02 g/L or less, more preferably 0.005 g/L or more and 0.01 g/L or less.
銦錫氫氧化物藉由雷射燒蝕在溶液中以原子、離子、團簇予以解離後在溶液中進行反應，且使平均粒徑變得小於照射雷射前之銦錫氫氧化物之平均粒徑，並且引起熱分解，而形成ITO奈米粉末。溶液中可由例如燒蝕電漿之發光確認是否產生燒蝕。 Indium tin hydroxide is reacted in solution by laser ablation in atoms, ions, and clusters, and the average particle diameter is made smaller than the average of indium tin hydroxide before irradiation. The particle size, and causes thermal decomposition, to form an ITO nanopowder powder. The presence or absence of ablation can be confirmed in the solution by, for example, the luminescence of the ablated plasma.
裝滿ITO粒子分散液之容器可自習知之容器材質、形狀等適當選則。且，在雷射光照射中，較好利用設置在容器內底部之攪拌構件攪拌ITO粒子分散溶液。作為攪拌構件可使用習知者，例如可舉出透過磁力攪拌器而設置之鐵氟龍(註冊商標)製轉子等。攪拌速度雖無特別限定，但較好為50~500rpm。且正要照射雷射光前之ITO粒子分散液之溫度較好為20~35℃。且照射雷射光中之溶液溫度較好為25~40℃。 The container filled with the ITO particle dispersion can be appropriately selected from the known container material and shape. Further, in the laser irradiation, the ITO particle dispersion solution is preferably stirred by a stirring member provided at the bottom of the container. As a stirring member, a conventional Teflon (registered trademark) rotor or the like provided through a magnetic stirrer can be used. The stirring speed is not particularly limited, but is preferably 50 to 500 rpm. The temperature of the ITO particle dispersion before the laser light is irradiated is preferably 20 to 35 °C. And the temperature of the solution in the irradiated laser light is preferably 25 to 40 °C.
以上述條件照射雷射光後，以透射電子顯微鏡觀察ITO奈米粉末時，照雷鐳射後之ITO奈米粉末分散液中，粉末之平均粒徑較好為1nm以上且30nm以下，更好為2nm以上且15nm以下。且若以電子束繞射評價照 射雷射後之ITO奈米粉末之結晶性，則亦有隨著雷射照射條件而異可獲得非晶質化之ITO奈米粉末之情況。如此，對分散有經雷射照射後所得之ITO奈米粉末之溶液進行固液分離，並進行乾燥，則可獲得本發明之ITO粒子。該ITO粒子之功函數可藉由改變上述銦錫氫氧化物粉末之分散溶液，或添加微量添加物加以控制。 After irradiating the laser light under the above conditions, when the ITO nanopowder powder is observed by a transmission electron microscope, the average particle diameter of the powder in the ITO nanoparticle dispersion liquid after laser irradiation is preferably 1 nm or more and 30 nm or less, more preferably 2 nm. Above and below 15 nm. And if the electron beam is diffracted The crystallinity of the ITO nanopowder after laser irradiation may also be obtained by amorphizing the ITO nanopowder powder depending on the laser irradiation conditions. Thus, the ITO particles of the present invention can be obtained by subjecting a solution obtained by dispersing the ITO nanopowder obtained by laser irradiation to solid-liquid separation and drying. The work function of the ITO particles can be controlled by changing the dispersion solution of the above indium tin hydroxide powder or by adding a trace amount of the additive.
(4)第4製造方法 (4) Fourth manufacturing method
丟棄以第1方法所得之銦錫共沉澱氫氧化物的沉澱物之上澄液，獲得漿料狀之銦錫氫氧化物後，在大氣中，較好在氮或氬等惰性氣體氛圍下，以100~200℃之範圍對該銦錫氫氧化物乾燥2~24小時後，在大氣中以250~800℃之範圍燒成0.5~6小時。利用錘式粉碎機或球磨機等對藉該燒成所形成之凝聚體進行粉碎並使之鬆散，獲得ITO粒子。利用噴磨機對該ITO粒子進行粉碎處理，使平均粒徑成為5~15nm之範圍。以下，與第1方法同樣，將該ITO粒子加入到使無水乙醇與蒸餾水混合之溶液中，使其含浸後，加入到玻璃皿中，並在氮氣氛圍下進行加熱，則能獲得本發明之ITO粒子。該ITO粒子之功函數可藉改變上述處理時間或溫度加以控制。 Discarding the precipitate on the precipitate of the indium tin coprecipitated hydroxide obtained by the first method to obtain a slurry of indium tin hydroxide, preferably in an atmosphere of an inert gas such as nitrogen or argon in the atmosphere. The indium tin hydroxide is dried in the range of 100 to 200 ° C for 2 to 24 hours, and then fired in the atmosphere at a temperature of 250 to 800 ° C for 0.5 to 6 hours. The aggregate formed by the firing is pulverized and loosened by a hammer mill or a ball mill to obtain ITO particles. The ITO particles were pulverized by a jet mill to have an average particle diameter of 5 to 15 nm. In the same manner as in the first method, the ITO particles are added to a solution in which anhydrous ethanol and distilled water are mixed, impregnated, added to a glass dish, and heated in a nitrogen atmosphere to obtain the ITO of the present invention. particle. The work function of the ITO particles can be controlled by changing the above processing time or temperature.
另外，本說明書中之ITO粒子之平均粒徑係指基於個數分佈之平均粒徑。且本發明中為200個之平均直徑。 In addition, the average particle diameter of the ITO particle in this specification means the average particle diameter based on the number distribution. And in the present invention, the average diameter is 200.
接著與比較例一起對本發明之實施例進行詳細說明。 Next, an embodiment of the present invention will be described in detail together with a comparative example.
首先，將含有18g的In金屬之氯化銦(InCl3)水溶液50mL與0.36g之氯化亞錫(SnCl2‧2H2O)混合，並在500mL水中同時滴入該混合水溶液與氨(NH3)水溶液，調整成pH7。在將溶液溫度設成30℃之狀態下使其反應30分鐘。以離子交換水反覆對所生成之銦錫共沉澱氫氧化物的沉澱物進行傾斜清洗。當上澄液之電阻率達到50000Ω‧cm以上時，捨棄上述沉澱物之上澄液，作成高黏度漿料狀，邊攪拌該漿料邊利用紫外線照射裝置(USHIO電機製Spot Cure SP-9)，選擇DeepUV類型，並使照射液面之中心照度達到50mW/cm2以上之方式照射5小時之紫外線。隨後，使漿料狀之銦錫氫氧化物在大氣中於110℃乾燥一晚，之後在大氣中以550℃燒成3小時，粉碎聚集體並使之鬆散，獲得約25g之ITO粉末。將該25g之ITO粉末加入到使無水乙醇與蒸餾水混合之溶液(混合比例為對於95質量份乙醇，蒸餾水為5質量份)中，使其含浸後，加入到玻璃皿中，並在氮氣氛圍下於330℃加熱2小時，獲得本發明之ITO粒子。 First, 50 mL of an indium chloride (InCl 3 ) aqueous solution containing 18 g of In metal was mixed with 0.36 g of stannous chloride (SnCl 2 ‧2H 2 O), and the mixed aqueous solution and ammonia (NH) were simultaneously dropped in 500 mL of water. 3 ) Aqueous solution, adjusted to pH 7. The reaction was allowed to proceed for 30 minutes while the temperature of the solution was set to 30 °C. The precipitate of the indium tin coprecipitated hydroxide formed was repeatedly washed with ion-exchanged water. When the resistivity of the upper liquid reaches 50,000 Ω ‧ cm or more, discard the above-mentioned sediment and make a high-viscosity slurry, and use the ultraviolet ray irradiation device while stirring the slurry (USHIO Electric Mechanism Spot Cure SP-9) The DeepUV type was selected, and the ultraviolet ray was irradiated for 5 hours in such a manner that the center illumination of the liquid surface was 50 mW/cm 2 or more. Subsequently, the slurry-like indium tin hydroxide was dried in the air at 110 ° C for one night, and then fired at 550 ° C for 3 hours in the atmosphere, and the aggregate was pulverized and loosened to obtain about 25 g of ITO powder. 25 g of the ITO powder was added to a solution in which absolute ethanol and distilled water were mixed (mixing ratio was 95 parts by mass of ethanol, and distilled water was 5 parts by mass), impregnated, and added to a glass dish under a nitrogen atmosphere. The ITO particles of the present invention were obtained by heating at 330 ° C for 2 hours.
將實施例1中對銦錫共沉澱氫氧化物漿料照射紫外線 時的聚光透鏡設定為標準類型，除此之外以與實施例1相同之方法進行，獲得本發明之ITO粒子。 The indium tin coprecipitated hydroxide slurry was irradiated with ultraviolet rays in Example 1. The concentrating lens of the present invention was obtained in the same manner as in Example 1 except that the condensing lens was set to a standard type.
將含有18g的In金屬之氯化銦(InCl3)水溶液50mL與0.6g氯化亞錫(SnCl2‧2H2O)混合，在500mL水中同時滴入該混合水溶液與氨(NH3)水溶液，調整為pH7。在使溶液溫度設成30℃之狀態下反應30分鐘。以離子交換水反覆對所生成之銦錫共沉澱氫氧化物的沉澱物進行傾斜清洗。當上澄液之電阻率達到50000Ω‧cm以上時，捨棄沉澱物之上澄液，獲得漿料狀之銦錫氫氧化物。以無水乙醇稀釋該漿料以使固體成分成為1.0%，並以氮氣充分置換於管之長邊方向垂直配置之管狀爐內之後，加熱至600℃，並在使載氣的N2氣體在管狀爐內部流通之狀態下，利用100kHz之超音波使漿料狀之銦錫氫氧化物霧化，對流通之N2氣體進行噴霧。此時之流通氣體流速設為0.5m/s。藉此，銦錫氫氧化物在管狀爐內熱分解，自管狀爐之排出口獲得本發明之ITO粒子。 50 mL of an indium chloride (InCl 3 ) aqueous solution containing 18 g of In metal was mixed with 0.6 g of stannous chloride (SnCl 2 ‧2H 2 O), and the mixed aqueous solution and the aqueous solution of ammonia (NH 3 ) were simultaneously dropped into 500 mL of water. Adjust to pH7. The reaction was carried out for 30 minutes while setting the temperature of the solution to 30 °C. The precipitate of the indium tin coprecipitated hydroxide formed was repeatedly washed with ion-exchanged water. When the resistivity of the supernatant liquid reaches 50,000 Ω ‧ cm or more, the supernatant on the precipitate is discarded to obtain a slurry of indium tin hydroxide. The slurry was diluted with absolute ethanol to have a solid content of 1.0%, and was sufficiently substituted with nitrogen gas in a tubular furnace vertically disposed in the longitudinal direction of the tube, and then heated to 600 ° C, and the carrier gas of N 2 gas was in a tubular shape. In the state where the inside of the furnace is circulated, the slurry-like indium tin hydroxide is atomized by ultrasonic waves of 100 kHz, and the circulating N 2 gas is sprayed. The flow rate of the flowing gas at this time was set to 0.5 m/s. Thereby, the indium tin hydroxide is thermally decomposed in the tubular furnace, and the ITO particles of the present invention are obtained from the discharge port of the tubular furnace.
丟棄實施例2所得之銦錫共沉澱氫氧化物的沉澱物之上澄液，獲得漿料狀之銦錫氫氧化物後，在大氣中，較好在氮或氬等惰性氣體氛圍下，以100~200℃之範圍對該銦錫氫氧化物乾燥15小時，獲得銦錫氫氧化物粉末。在石 英玻璃製容器中加入以固體成分1.0%在乙醇中超音波分散該銦錫氧化物粉末而成之分散溶液，邊以磁力攪拌器攪拌邊照射藉Nd：YAG雷射振盪之266nm之雷射光。關於雷射光，作為每1脈衝之強度設為100mJ(100mJ/脈衝)，雷射光之脈衝寬度設為20ns，峰值(峰值功率)設為100MW，並將雷射之振盪頻率(脈衝週期)設為30Hz。對分散有照射該雷射後所得之ITO奈米粉末的溶液進行固液分離，並進行乾燥，藉此獲得本發明之ITO粒子。 Discarding the precipitate of the indium tin coprecipitated hydroxide obtained in Example 2 to obtain a slurry of indium tin hydroxide, and then in the atmosphere, preferably under an inert gas atmosphere such as nitrogen or argon, The indium tin hydroxide was dried for 15 hours in the range of 100 to 200 ° C to obtain an indium tin hydroxide powder. In the stone To the glass container, a dispersion solution obtained by ultrasonically dispersing the indium tin oxide powder in a solid content of 1.0% in ethanol was added, and a 266 nm laser light by a Nd:YAG laser oscillation was irradiated while stirring with a magnetic stirrer. Regarding the laser light, the intensity per pulse is set to 100 mJ (100 mJ/pulse), the pulse width of the laser light is set to 20 ns, the peak value (peak power) is set to 100 MW, and the oscillation frequency (pulse period) of the laser is set to 30Hz. The ITO particles of the present invention are obtained by subjecting a solution in which the ITO nanopowder powder obtained by irradiating the laser is dispersed to a solid-liquid separation and drying.
丟棄實施例2所得之銦錫共沉澱氫氧化物的沉澱物之上澄液，獲得漿料狀之銦錫氫氧化物後，在大氣中於110℃對該銦錫氫氧化物乾燥15小時後，在大氣中於600℃燒成3小時。利用錘式粉碎機或球磨機等對藉該燒成所形成之凝聚體進行粉碎並使之鬆散，獲得ITO粒子。利用噴磨機對該ITO粒子進行粉碎處理，使平均粒徑成為5~15nm之範圍。以下，與第1方法同樣地，將該ITO粒子加入到使無水乙醇與蒸餾水混合之溶液中，使其含浸後，加入到玻璃皿中，並在氮氣氛圍下以400℃加熱5小時，獲得本發明之ITO粒子。 Discarding the precipitate of the indium tin coprecipitated hydroxide obtained in Example 2 to obtain a slurry of indium tin hydroxide, and drying the indium tin hydroxide at 110 ° C for 15 hours in the atmosphere. It was baked at 600 ° C for 3 hours in the atmosphere. The aggregate formed by the firing is pulverized and loosened by a hammer mill or a ball mill to obtain ITO particles. The ITO particles were pulverized by a jet mill to have an average particle diameter of 5 to 15 nm. In the same manner as in the first method, the ITO particles were added to a solution in which absolute ethanol and distilled water were mixed, impregnated, and then added to a glass dish, and heated at 400 ° C for 5 hours in a nitrogen atmosphere to obtain the present. Inventive ITO particles.
實施例5之製造方法中，除將加熱條件設定為 250℃、1小時之外，餘與實施例5相同之方法進行，獲得本發明之ITO粒子。 In the manufacturing method of Example 5, except that the heating condition is set to The same procedure as in Example 5 was carried out at 250 ° C for 1 hour to obtain ITO particles of the present invention.
將200g的In金屬加入到600cm3的12N-HCl中使其完全溶解，製備氯化銦溶液。在該氯化銦溶液中加入33g的SnCl4之60質量%水溶液，製備InCl3-SnCl4(Sn/In比：0.05)混合溶液。接著，在離子交換水中溶解550g碳酸銨，調製成液量：4.5dm3、溫度：30℃。於約20分鐘邊攪拌邊將所有InCl3-SnCl4液滴入於該碳酸銨水溶液中，生成共沉澱物，以此狀態再攪拌30分鐘。此時之反應液體之最終pH為4.5。回收共沉澱物並以離心分離機進行脫水後，加入離子交換水邊清洗並進行離心過濾，當濾液之比電阻達到5000Ω‧cm以上時，結束離心過濾。接著使該共沉澱物在100℃下乾燥一晚後，以600℃進行3小時之加熱分解並粉碎，獲得比較例1之氧化銦錫粉末：213g。 200 g of In metal was added to 600 cm 3 of 12N-HCl to completely dissolve it, and an indium chloride solution was prepared. To the indium chloride solution, 33 g of a 60% by mass aqueous solution of SnCl 4 was added to prepare a mixed solution of InCl 3 -SnCl 4 (Sn/In ratio: 0.05). Next, 550 g of ammonium carbonate was dissolved in ion-exchanged water to prepare a liquid amount: 4.5 dm 3 and a temperature of 30 °C. All of InCl 3 -SnCl 4 was dropped into the aqueous solution of ammonium carbonate with stirring for about 20 minutes to form a coprecipitate, and the mixture was further stirred for 30 minutes. The final pH of the reaction liquid at this time was 4.5. After the coprecipitate was recovered and dehydrated by a centrifugal separator, it was washed with ion-exchanged water and centrifuged, and when the specific resistance of the filtrate reached 5,000 Ω·cm or more, the centrifugal filtration was terminated. Then, the coprecipitate was dried at 100 ° C for one night, and then thermally decomposed and pulverized at 600 ° C for 3 hours to obtain Indium Tin Oxide powder of Comparative Example 1 : 213 g.
於實施例1~6及比較例1所得之各ITO粒子之功函數係藉以下方法測定。首先，將ITO粒子放入直徑10mm、深度1mm之平盤狀不銹鋼製粒子固定器中之後，使用載波片，以不弄碎ITO粒子之方式壓縮ITO粒子，並以填充密度達到2~3g/cm3之方式填充於粒子固定器 中。在60℃之乾燥機內對其進行1小時以上之乾燥並自ITO粒子去除吸附的水分。含水率為0.8%。從粒子固定器中取出ITO粒子的壓縮體，在室溫放置5分鐘使其冷卻，並在5分鐘內測定接觸電位差。測定係以開爾文探針(KP Technology公司製造；型號SKP 020)，使用經鍍金之探頭進行，並將50次累計的測定重複進行3次，且求出與電鍍於其探頭上之金的接觸電位差之平均值，將該接觸電位差之平均值與金的功函數(5.10eV)之和作為ITO粒子之功函數。結果示於下表1。 The work functions of the respective ITO particles obtained in Examples 1 to 6 and Comparative Example 1 were measured by the following methods. First, after the ITO particles were placed in a flat disk-shaped stainless steel particle holder having a diameter of 10 mm and a depth of 1 mm, the ITO particles were compressed by using a carrier sheet so as not to crush the ITO particles, and the packing density was 2 to 3 g/cm. The way of 3 is filled in the particle holder. It was dried in a dryer at 60 ° C for 1 hour or more and the adsorbed moisture was removed from the ITO particles. The water content was 0.8%. The compressed body of the ITO particles was taken out from the particle holder, left to stand at room temperature for 5 minutes, and cooled, and the contact potential difference was measured within 5 minutes. The measurement was performed with a Kelvin probe (manufactured by KP Technology Co., Ltd.; model SKP 020) using a gold-plated probe, and the 50 cumulative measurements were repeated three times, and the contact potential difference with the gold plated on the probe was determined. The average value is the sum of the contact potential difference and the work function of gold (5.10 eV) as a work function of the ITO particles. The results are shown in Table 1 below.
將20g之於實施例1~6及比較例1所得之各ITO粒子加入以下混合液中並分散，該混合液中含有蒸餾水(0.020g)、三乙二醇-二-2-己酸乙酯[3G](23.8g)、無水乙醇(2.1g)、磷酸聚酯(1.0g)、2-乙基己酸(2.0g)、2,4-戊二酮(0.5g)。以無水乙醇將所製備之分散液稀釋至固體成分即ITO粒子之含量達到10質量%為止。以旋塗法將該稀釋之分散液塗佈於石英玻璃板上進行成膜，獲得厚度0.2μm之ITO透明導電膜。 20 g of each of the ITO particles obtained in Examples 1 to 6 and Comparative Example 1 was added to and dispersed in the following mixed solution containing distilled water (0.020 g) and triethylene glycol-di-2-hexanoate ethyl ester. [3G] (23.8 g), absolute ethanol (2.1 g), phosphoric acid polyester (1.0 g), 2-ethylhexanoic acid (2.0 g), 2,4-pentanedione (0.5 g). The prepared dispersion liquid was diluted with anhydrous ethanol until the content of the solid component, that is, the ITO particles was 10% by mass. The diluted dispersion was applied onto a quartz glass plate by a spin coating method to form a film, and an ITO transparent conductive film having a thickness of 0.2 μm was obtained.
由實施例1~6及比較例1所得之各ITO粒子製備ITO導電膜塗料，且以濕式塗佈法將該塗料塗佈於超直型薄膜太陽能電池之光電轉換層亦即發電層上，形成透明導 電膜。該太陽能電池係在透明玻璃基板上藉由由FTO(摻氟SnO2)所成之另一透明導電膜、光電轉換層(發電層)、上述透明導電膜及導電性反射膜所構成。在上面形成背面電極。 An ITO conductive film coating was prepared from each of the ITO particles obtained in Examples 1 to 6 and Comparative Example 1, and the coating was applied to a photoelectric conversion layer, that is, a power generation layer of an ultra-straight thin film solar cell, by a wet coating method. A transparent conductive film is formed. This solar cell is composed of a transparent conductive film made of FTO (fluorine-doped SnO 2 ), a photoelectric conversion layer (power generation layer), the above transparent conductive film, and a conductive reflective film on a transparent glass substrate. A back electrode is formed on the surface.
藉下列方法製備導電膜塗料。即添加1.0質量%之於實施例1~6及比較例1所得之各ITO粒子、0.2質量%之使矽酸乙酯水解而成之矽氧烷聚合物作為黏合劑、0.01質量%之下式(1)所示之有機偶合劑作為偶合劑，再添加乙醇作為分散介質，藉此使整體成為100質量%。以DYNO-MILL(橫式珠磨機)，使用直徑0.3mm之氧化鋯球研磨該混合物，使該研磨機運轉兩小時，從而將ITO粒子分散於混合物中，藉此製備導電膜塗料。 A conductive film coating was prepared by the following method. In other words, 1.0% by mass of each of the ITO particles obtained in Examples 1 to 6 and Comparative Example 1 and 0.2% by mass of a siloxane polymer obtained by hydrolyzing ethyl decanoate as a binder, 0.01% by mass or less (1) The organic coupling agent shown is used as a coupling agent, and ethanol is further added as a dispersion medium, whereby the whole is made 100% by mass. The ITO particles were ground in a DYNO-MILL (horizontal bead mill) using a zirconia ball having a diameter of 0.3 mm, and the ITO particles were dispersed in the mixture to prepare a conductive film coating.
接著，利用旋塗法在經成膜之發電層上塗佈上述導電膜塗料，以使燒成後之膜厚成為80nm，且於200℃對塗膜進行30分鐘燒粘，形成背面側之透明導電膜。燒成後之膜厚係藉由以SEM拍攝截面之照片進行測定。經燒成所得之背面側之透明導電膜中之ITO粒子與黏合劑之比例即ITO粒子/黏合劑之比為2/1。另外，關於燒成溫度係設為測定10cm見方之玻璃基板之角部四點之溫 度，使平均值落入設定溫度(200℃)±5℃的範圍內之條件。 Next, the conductive film coating material was applied onto the film-formed power generation layer by a spin coating method so that the film thickness after firing was 80 nm, and the coating film was baked at 200 ° C for 30 minutes to form a transparent surface on the back side. Conductive film. The film thickness after firing was measured by photographing the cross section by SEM. The ratio of the ITO particles to the binder in the transparent conductive film on the back side obtained by firing, that is, the ratio of the ITO particles/adhesive agent was 2/1. In addition, the firing temperature is set to a temperature of four points at the corner of the glass substrate of 10 cm square. The condition is such that the average value falls within the range of the set temperature (200 ° C) ± 5 ° C.
另外，以旋塗法在所形成之背面側透明導電膜上塗佈將平均粒徑為0.03μm之Ag膠體分散於乙醇溶劑中而成之Ag奈米墨水，使燒成後之膜厚成為200nm，在200℃對塗膜進行30分鐘燒烤而形成背面側之反射電極膜。藉此獲得評價用多接合型薄膜矽太陽能電池。 Further, an Ag nano ink obtained by dispersing an Ag colloid having an average particle diameter of 0.03 μm in an ethanol solvent was applied onto the formed back surface transparent conductive film by a spin coating method to have a film thickness of 200 nm after firing. The coating film was baked at 200 ° C for 30 minutes to form a reflective electrode film on the back side. Thereby, a multi-junction type thin film tantalum solar cell for evaluation was obtained.
於對以上述方法獲得之評價用多接合型薄膜矽太陽能電池之太陽能電池單元進行線加工後之基板上佈置導線，並利用太陽光模擬器與數位電錶，獲得照射AM：1.5、100mW/cm2之光時之I-V(電流-電壓)曲線。將該曲線中最佳動作點之電壓設為Vm、電流設為Im，求出最大電力Vm×Im，另一方面，求出該曲線之電壓最大值的開放電壓VOC與電流之最大值的短路電流ISC，並根據(Vm×Im)/(VOC×ISC)計算曲線因子。將該曲線因子示於表1及圖1。 Arranging the wires on the substrate after the wire processing of the solar cell of the multi-junction type thin film solar cell obtained by the above method, and using the solar simulator and the digital electric meter to obtain the irradiation AM: 1.5, 100 mW/cm 2 The IV (current-voltage) curve of the light. The voltage at the optimum operating point in the curve is V m , the current is I m , and the maximum power V m ×I m is obtained. On the other hand, the open voltage V OC and current of the voltage maximum of the curve are obtained. The short-circuit current I SC of the maximum value is calculated, and the curve factor is calculated according to (V m × I m ) / (V OC × I SC ). The curve factors are shown in Table 1 and Figure 1.
此外藉由將所得之I-V(電流-電壓)曲線中之電流值(I)除以薄膜太陽能電池單元之表面積求出J-V(電流密度-電壓)曲線。該J-V曲線中，將電壓之軸與電流密度之軸作為兩邊，將連結原點與J-V曲線上之點所畫出之長 方形面積達到最大時之面積中之輸出功率設為最高輸出密度(mW/cm2)，並將[最高輸出密度(mW/cm2)]/[100(mW/cm2)]×100設為發電層之轉換效率。將利用包含實施例1~6及比較例1之ITO粒子之透明導電膜之太陽能電池的發電層之轉換效率示於表1。 Further, a JV (current density-voltage) curve was obtained by dividing the current value (I) in the obtained IV (current-voltage) curve by the surface area of the thin film solar cell. In the JV curve, the axis of the voltage and the axis of the current density are used as the two sides, and the output power in the area where the rectangular area drawn by the point connecting the origin and the point on the JV curve is maximized is set as the highest output density (mW/). Cm 2 ), and [highest output density (mW/cm 2 )] / [100 (mW/cm 2 )] × 100 is set as the conversion efficiency of the power generation layer. The conversion efficiency of the power generation layer of the solar cell using the transparent conductive film of the ITO particles of Examples 1 to 6 and Comparative Example 1 is shown in Table 1.
由表1明確可知，比較例1之ITO粒子中，ITO粒子之功函數為5.33eV，相對於此，實施例1~6之ITO粒子中，可將ITO粒子之功函數控制在4.80~5.30之範圍內。並且，由表1及圖1明確可知，對於作為太陽能電池之性能，可判定為與比較例1相比，實施例1~6之曲線因子較高，且轉換效率較優異。 As is clear from Table 1, in the ITO particles of Comparative Example 1, the work function of the ITO particles was 5.33 eV. In contrast, in the ITO particles of Examples 1 to 6, the work function of the ITO particles can be controlled to 4.80 to 5.30. Within the scope. Further, as is clear from Table 1 and FIG. 1, it can be determined that the performance of the solar cell is higher than that of Comparative Example 1, and the curve factors of Examples 1 to 6 are high, and the conversion efficiency is excellent.
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| GB201011118D0 (en) * | 2010-06-30 | 2010-08-18 | Univ Warwick | Transparent electrodes for semiconductor thin film devices |
| JP5582962B2 (en) * | 2010-10-25 | 2014-09-03 | 東海旅客鉄道株式会社 | Method for forming transparent conductive film |
| SG193253A1 (en) * | 2011-03-04 | 2013-10-30 | Cambrios Technologies Corp | Method of tuning work function of metal nanostructure-based transparent conductor |
| WO2012122387A1 (en) * | 2011-03-10 | 2012-09-13 | Marshall Cox | Graphene electrodes for electronic devices |
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2013
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- 2013-11-29 TW TW102143768A patent/TWI614216B/en active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102201274A (en) * | 2010-03-26 | 2011-09-28 | 三菱综合材料株式会社 | Conductive film forming composition, solar cell composite film and forming method thereof |
| CN102211786A (en) * | 2011-03-02 | 2011-10-12 | 北京冶科纳米科技有限公司 | Preparation method of nanoscale indium tin oxide powder |
| CN102786080A (en) * | 2012-07-18 | 2012-11-21 | 中国科学院福建物质结构研究所 | Indium tin oxide compound, its preparation method and its photocatalytic application |
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| TW201434754A (en) | 2014-09-16 |
| JP6201345B2 (en) | 2017-09-27 |
| CN104036843B (en) | 2017-08-25 |
| JP2014175385A (en) | 2014-09-22 |
| CN104036843A (en) | 2014-09-10 |
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