JP2015020932A - Method for producing chalcopyrite nanoparticle - Google Patents

Method for producing chalcopyrite nanoparticle Download PDF

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JP2015020932A
JP2015020932A JP2013150685A JP2013150685A JP2015020932A JP 2015020932 A JP2015020932 A JP 2015020932A JP 2013150685 A JP2013150685 A JP 2013150685A JP 2013150685 A JP2013150685 A JP 2013150685A JP 2015020932 A JP2015020932 A JP 2015020932A
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JP2015020932A5 (en
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克昭 菅沼
Katsuaki Suganuma
克昭 菅沼
徹 菅原
Toru Sugahara
徹 菅原
金▲てい▼ 酒
Jinting Jiu
金▲てい▼ 酒
シンハ マンジート
Singh Manjeet
シンハ マンジート
俊博 曽
Chun-Bor Tseng
俊博 曽
租偉 翁
Chu Wei Weng
租偉 翁
卓磨 吉川
Takuma Yoshikawa
卓磨 吉川
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TAIYODENCHI SOGO KENKYUSHO KK
Osaka University NUC
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TAIYODENCHI SOGO KENKYUSHO KK
Osaka University NUC
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Priority to PCT/JP2014/069197 priority patent/WO2015008858A1/en
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

PROBLEM TO BE SOLVED: To provide a method capable of producing chalcopyrite nanoparticles having a small and uniform particle diameter easily in a large amount.SOLUTION: There is provided a method for producing chalcopyrite nanoparticles by mixing and heating a Group I metal compound, a Group III metal compound and a Group IV metal element in the periodic table in an amine-based solvent to react the Group IV metal element with the Group I metal compound and the Group III metal compound. Since the heating step comprises a first temperature raising step for raising a temperature from room temperature to 100°C at a first temperature raising rate and a second temperature raising step for raising a temperature from 100°C to 200°C at a second temperature raising rate lower than the first temperature raising rate, uniform chalcopyrite nanoparticles having a small and uniform particle diameter can be obtained.

Description

本発明は、化合物太陽電池に用いられるカルコパイライトナノ粒子の製造方法に関する。   The present invention relates to a method for producing chalcopyrite nanoparticles used in compound solar cells.

化合物太陽電池とは、複数の元素から成る化合物半導体から形成された光吸収層を備えた太陽電池をいう。化合物太陽電池に用いられる化合物半導体の代表的なものとして、周期律表のIII族とV族の組み合わせ（GaAs、GaP、InP等）、II族とVI族の組み合わせ（CdTe、ZnSe等）、IV族同士の組み合わせ（SiC）、 I族とIII族とVI族の組み合わせ（CuInSe、CuInGaSe）からなる化合物半導体が挙げられる。CuInSeやCuInGaSeは、その結晶構造が黄銅鉱に似ていることから、カルコパイライト系化合物半導体とも呼ばれる。また、化合物半導体を構成する元素記号から、CIS系化合物半導体、CIGS系化合物半導体とも呼ばれている。これらの化合物半導体を用いた太陽電池は、Si系の太陽電池に比べて遜色ない変換効率を示すだけでなく、製造方法が簡単で、素子に使用する膜厚が薄く原料の省資源化につながる。また、原料に要求される純度が低い事や放射線への高い安定性も言及されており、近年、著しい注目を集めている。   A compound solar cell refers to a solar cell provided with a light absorption layer formed from a compound semiconductor composed of a plurality of elements. Typical compound semiconductors used in compound solar cells are combinations of groups III and V of the periodic table (GaAs, GaP, InP, etc.), combinations of groups II and VI (CdTe, ZnSe, etc.), IV Examples include compound semiconductors composed of combinations of groups (SiC) and combinations of groups I, III and VI (CuInSe, CuInGaSe). CuInSe and CuInGaSe are also called chalcopyrite compound semiconductors because their crystal structures resemble chalcopyrite. Moreover, it is also called a CIS-based compound semiconductor or a CIGS-based compound semiconductor from the element symbols constituting the compound semiconductor. Solar cells using these compound semiconductors not only have conversion efficiency comparable to Si-based solar cells, but also have a simple manufacturing method and a thin film used for the device, leading to resource savings in raw materials. . In addition, low purity required for raw materials and high stability to radiation are also mentioned, and in recent years it has attracted considerable attention.

従来、化合物半導体から光吸収層を形成する方法としては、加熱蒸着法やスパッタリング法が用いられていた。ところが、これらの方法は超高真空環境下で行わなければならず、高価な製造設備が必要となることから、近年、安価な設備で製造できる方法が提案されている。その一つに、カルコパイライト系化合物半導体のナノ粒子を形成し、このナノ粒子を用いて光吸収層を製造する方法がある。   Conventionally, as a method for forming a light absorption layer from a compound semiconductor, a heating vapor deposition method or a sputtering method has been used. However, these methods must be performed in an ultra-high vacuum environment and require expensive manufacturing equipment, and in recent years, methods that can be manufactured with inexpensive equipment have been proposed. One of them is a method of forming a chalcopyrite compound semiconductor nanoparticle and manufacturing a light absorption layer using the nanoparticle.

例えば、特許文献１〜３には、CuInSe化合物（CIS系化合物半導体）やCuInGaSe化合物（CIGS系化合物半導体）を構成する元素の塩と金属塩を反応させることによりカルコパイライトナノ粒子を形成する方法が記載されている。   For example, Patent Documents 1 to 3 disclose a method of forming chalcopyrite nanoparticles by reacting a metal salt with a salt of an element constituting a CuInSe compound (CIS compound semiconductor) or a CuInGaSe compound (CIGS compound semiconductor). Have been described.

特開2012-79770号公報JP 2012-79770 JP 特開2012-49358号公報JP 2012-49358 特開2012-33728号公報JP 2012-33728 A

特許文献１〜３に記載されている方法では、アニリンやアルコールアミン、エチレンジアミン等の有機溶媒にCu、In、及びGaのハロゲン化物とSe単体を溶解して原料溶液を作製し、該原料溶液を加熱して、Cu、In、及びGaのハロゲン化物とSe単体を反応させることによりナノ粒子を形成している。この場合、原料溶液の加熱は１５０℃〜２００℃で１分間〜２０時間行うとされている。
Cu、In、及びGaのハロゲン化物とSe単体の反応は２００℃付近で進行する。従って、加熱時間が短いと、反応が十分に進まず、均一なナノ粒子を得ることができない。一方、加熱時間が長いとナノ粒子が成長するため、得られるナノ粒子の粒径が大きくなる。また、原料溶液の作製は、通常、室温下で行われる。従って、室温状態の原料溶液を一定の速度で急速に１５０℃〜２００℃まで昇温させると、ナノ粒子の成長過程の相状態をうまくコントロールすることができず、均一な粒径のナノ粒子を得ることが難しい。光吸収層の光電変換効率を上げるためには、緻密な半導体膜を形成する必要があるが、ナノ粒子の粒径が大きかったり、粒径が不均一であったりすると、緻密な半導体膜を形成することができない。 In the methods described in Patent Documents 1 to 3, a raw material solution is prepared by dissolving Cu, In, and Ga halides and Se alone in an organic solvent such as aniline, alcohol amine, and ethylene diamine. Nanoparticles are formed by heating and reacting Cu, In, and Ga halides with Se alone. In this case, heating of the raw material solution is performed at 150 ° C. to 200 ° C. for 1 minute to 20 hours.
The reaction of Cu, In, and Ga halides with Se alone proceeds at around 200 ° C. Therefore, when the heating time is short, the reaction does not proceed sufficiently and uniform nanoparticles cannot be obtained. On the other hand, when the heating time is long, the nanoparticles grow, so that the obtained nanoparticles have a large particle size. The production of the raw material solution is usually performed at room temperature. Therefore, if the temperature of the raw material solution at room temperature is rapidly increased to 150 ° C. to 200 ° C. at a constant rate, the phase state of the nanoparticle growth process cannot be controlled well, and nanoparticles with a uniform particle size are Difficult to get. In order to increase the photoelectric conversion efficiency of the light absorption layer, it is necessary to form a dense semiconductor film. However, if the particle size of the nanoparticles is large or the particle size is not uniform, a dense semiconductor film is formed. Can not do it.

本発明が解決しようとする課題は、粒径が小さく且つ粒径が均一なカルコパイライトナノ粒子を簡単に製造することができる製造方法を提供することである。   The problem to be solved by the present invention is to provide a production method capable of easily producing chalcopyrite nanoparticles having a small particle size and a uniform particle size.

上記課題を解決するために成された本発明は、周期律表の第I族金属化合物、第III族金属化合物、及び第VI族金属の単体をアミン系溶媒中に入れて混合し、加熱して、前記第I族金属化合物及び前記第III族金属化合物と、前記第VI族金属の単体を反応させることによりカルコパイライトナノ粒子を製造する方法であって、
加熱する工程が、
第１昇温速度で室温から１００℃まで昇温する第１昇温工程と、
前記第１昇温速度よりも遅い第２昇温速度で１００℃から２００℃まで昇温する第２昇温工程と
を有することを特徴とする。 The present invention, which has been made to solve the above-mentioned problems, comprises mixing a group I metal compound, group III metal compound, and group VI metal simple substance in the periodic table in an amine solvent, heating the mixture. A method of producing chalcopyrite nanoparticles by reacting the Group I metal compound and the Group III metal compound with the Group VI metal alone,
The heating process is
A first temperature raising step for raising the temperature from room temperature to 100 ° C. at a first temperature raising rate;
And a second temperature raising step of raising the temperature from 100 ° C. to 200 ° C. at a second temperature raising rate slower than the first temperature raising rate.

上記の製造方法においては、さらに、第２昇温工程が、１００℃から１５０℃まで昇温する前期工程と、該前期工程よりも遅い昇温速度で１５０℃から２００℃まで昇温する後期工程から構成されていることが好ましい。このように、第２昇温工程を細分化することにより、カルコパイライトナノ粒子の大きさを制御しやすくなる。さらに、カルコパイライトナノ粒子の大きさも制御しやすくなるという効果もある。   In the above manufacturing method, the second temperature raising step further includes a first step in which the temperature is raised from 100 ° C. to 150 ° C., and a latter step in which the temperature is raised from 150 ° C. to 200 ° C. at a temperature raising rate slower than the first step. It is preferable that it is comprised from these. Thus, it becomes easy to control the size of the chalcopyrite nanoparticles by subdividing the second temperature raising step. Furthermore, there is an effect that the size of chalcopyrite nanoparticles can be easily controlled.

さらに、本発明に係るカルコパイライトナノ粒子の製造方法は、前記第２昇温速度よりも遅い第３昇温速度で２００℃から２５０℃まで昇温する第３昇温工程を有することが好ましい。２００℃から２５０℃までゆっくりとした速度で昇温する第３昇温工程では、第I族金属化合物、第III族金属化合物、及び第VI族金属の単体とアミン系溶媒との反応が安定的に進行するため、均一なカルコパイライトナノ粒子を得ることができる。   Furthermore, the method for producing chalcopyrite nanoparticles according to the present invention preferably includes a third temperature raising step of raising the temperature from 200 ° C. to 250 ° C. at a third temperature raising rate that is slower than the second temperature raising rate. In the third heating step, where the temperature is raised from 200 ° C. to 250 ° C. at a slow rate, the reaction between the group I metal compound, the group III metal compound, and the group VI metal simple substance and the amine solvent is stable. Therefore, uniform chalcopyrite nanoparticles can be obtained.

本発明の方法では、第I族と第III族の金属化合物と第VI族金属の単体を有機溶媒中に入れて混合した後、加熱する工程において、最初は昇温速度を速くして反応を進め、反応が進んだ段階で昇温速度を遅くして安定的に反応させるようにしたため、粒径が小さく且つ粒径の揃った均一なカルコパイライトナノ粒子を得ることができる。また、安定的に反応させることができる結果、カルコパイライト粒子の大量製造が可能となる。さらに、加熱する工程を少なくとも２つの工程から構成したため、各工程における昇温速度を調整することにより、得られるカルコパイライトナノ粒子のサイズだけでなく、元素組成や形状を自由に制御することができる。   In the method of the present invention, the group I and group III metal compound and the group VI metal simple substance are mixed in an organic solvent and then heated. As the reaction proceeds, the temperature rise rate is slowed down and the reaction is stably performed, so that uniform chalcopyrite nanoparticles having a small particle size and a uniform particle size can be obtained. Moreover, as a result of being able to make it react stably, the mass production of chalcopyrite particle | grains is attained. Furthermore, since the heating step is composed of at least two steps, not only the size of the obtained chalcopyrite nanoparticles but also the elemental composition and shape can be freely controlled by adjusting the temperature increase rate in each step. .

製造例１における製造手順の概略図。Schematic of the manufacturing procedure in the manufacture example 1. FIG. 製造例１の第１工程から第３（前期）工程までの各工程におけるナノ粒子の走査型電子顕微鏡（ＳＥＭ）写真。The scanning electron microscope (SEM) photograph of the nanoparticle in each process from the 1st process of manufacture example 1 to the 3rd (pre-term) process. 第３（後期）工程におけるナノ粒子のＳＥＭ写真。The SEM photograph of the nanoparticle in the 3rd (late stage) process. 図２に示すナノ粒子のＸＲＤ解析結果。The XRD analysis result of the nanoparticle shown in FIG. 図３に示すナノ粒子のＸＲＤ解析結果。The XRD analysis result of the nanoparticle shown in FIG. 製造例２の実験１におけるＳＥＭ写真（ａ）及びＴＧＡ解析結果（ｂ）。The SEM photograph (a) and TGA analysis result (b) in Experiment 1 of manufacture example 2. 製造例２の実験２におけるＳＥＭ写真（ａ）及びＴＧＡ解析結果（ｂ）。The SEM photograph (a) and TGA analysis result (b) in Experiment 2 of manufacture example 2. 製造例２の実験３におけるＳＥＭ写真（ａ）及びＴＧＡ解析結果（ｂ）。The SEM photograph (a) and TGA analysis result (b) in Experiment 3 of manufacture example 2. 実験１〜３で得られるナノ粒子のＸＲＤ解析結果。The XRD analysis result of the nanoparticle obtained in Experiments 1-3. 溶媒としてＰＤＡを用いた場合のＳＥＭ写真。The SEM photograph at the time of using PDA as a solvent. ＴＧＡ解析結果及びＸＲＤ解析結果。TGA analysis result and XRD analysis result.

本発明は、周期律表の第I族金属化合物、第III族金属化合物、及び第VI族金属の単体を原料とし、これら原料とアミン系溶媒を混合して段階的に温度を上げながら加熱することにより原料とアミン系溶媒を反応させ、カルコパイライトナノ粒子（以下、「ナノ粒子」ともいう。）を製造する方法である。   The present invention uses a group I metal compound, a group III metal compound, and a group VI metal in the periodic table as raw materials, mixes these raw materials and an amine solvent, and heats them while raising the temperature stepwise. Thus, the raw material and the amine solvent are reacted to produce chalcopyrite nanoparticles (hereinafter also referred to as “nanoparticles”).

本発明の製造方法では、アミン系溶媒は原料の分散剤及び還元剤として作用する。このとき、原料とアミン系溶媒の反応温度である２００℃付近まで、少なくとも２つの昇温工程により段階的に温度を上げることにより、ナノ粒子の成長過程の相状態を制御し、得られるナノ粒子の形状や大きさを自在に変化させることができる。特に、本発明では、１００℃まで昇温する速度を相対的に速く、１００℃から２００℃まで昇温する速度を相対的に遅くすることにより、ナノ粒子の過度な成長を抑えつつ安定的に反応させるようにしたため、粒径が小さく、且つ、粒径の揃ったナノ粒子を大量に得ることができる。   In the production method of the present invention, the amine solvent acts as a raw material dispersant and reducing agent. At this time, the phase state of the nanoparticle growth process is controlled by increasing the temperature stepwise by at least two heating steps up to about 200 ° C., which is the reaction temperature between the raw material and the amine solvent, and the resulting nanoparticles The shape and size can be changed freely. In particular, in the present invention, the rate of temperature increase to 100 ° C. is relatively high, and the rate of temperature increase from 100 ° C. to 200 ° C. is relatively slow, thereby stably suppressing excessive growth of nanoparticles. Since the reaction is performed, a large amount of nanoparticles having a small particle size and a uniform particle size can be obtained.

しかも、複数の昇温工程を経て２００℃まで加熱するようにしたため、各昇温工程における昇温速度をそれぞれ独立的に制御することができ、ナノ粒子の成長過程の相状態の制御の自由度が増す。このため、ナノ粒子の形状や大きさをより一層自在に変化させることができる。   In addition, since heating is performed up to 200 ° C. through a plurality of temperature raising steps, the temperature raising rate in each temperature raising step can be controlled independently, and the degree of freedom in controlling the phase state of the nanoparticle growth process. Increase. For this reason, the shape and size of the nanoparticles can be changed more freely.

本発明では、第I族金属化合物としてはCu化合物が好適に用いられるが、これ以外の例えばAg化合物を用いることもできる。また、第III族金属化合物としては、In又は／及びGa化合物を用いることが好ましい。これら第I族金属化合物、第III族金属化合物としては、CuCl、InCl3、Ga(Cl)3等のハロゲン化物が好適であるが、この他、酢酸塩、硝酸塩、塩酸塩や金属錯体を用いることができる。 In the present invention, a Cu compound is preferably used as the Group I metal compound, but other compounds such as an Ag compound can also be used. Further, as the Group III metal compound, it is preferable to use In or / and a Ga compound. As these Group I metal compounds and Group III metal compounds, halides such as CuCl, InCl 3 , Ga (Cl) 3 are suitable, but in addition, acetates, nitrates, hydrochlorides and metal complexes are used. be able to.

第VI族金属の単体としてはSe粉末が好適に用いられるが、硫黄（S）の粉末でも良い。
アミン系溶媒としては、ドデシル・アミンやペンタジル・アミン等、種々のアミンを用いることができるが、ドデシル・アミンは他のアミンに比べてメタノール系溶媒やトルエンを用いて完全に除去できる点、分解温度が低い点で他のアミンよりも優れており、溶媒にドデシル・アミンを用いた場合は、粒径の小さなナノ粒子を高収率で得ることができる。 Se powder is suitably used as the group VI metal simple substance, but sulfur (S) powder may also be used.
Various amines such as dodecyl amine and pentazyl amine can be used as the amine solvent, but the dodecyl amine can be completely removed using a methanol solvent or toluene as compared with other amines. It is superior to other amines in that the temperature is low, and when dodecylamine is used as the solvent, nanoparticles having a small particle size can be obtained in a high yield.

以下、本発明に係るナノ粒子の具体的な製造方法を、いくつかの製造例を参照しながら説明する。
［製造例１］
製造例１は、第I族金属化合物としてはCuClを、第III族金属化合物としてInCl3とGa(acac)3（アセチルアセトンガリウム）を、第VI族金属の単体としてはSe粉末を、アミン系溶媒としてドデシル・アミン（ＤＤＡ）を用いた例である。具体的には、以下の製造手順から成る。 Hereinafter, a specific method for producing nanoparticles according to the present invention will be described with reference to several production examples.
[Production Example 1]
Production Example 1 includes CuCl as the Group I metal compound, InCl 3 and Ga (acac) 3 (acetylacetone gallium) as the Group III metal compound, Se powder as the Group VI metal alone, and an amine solvent. As an example using dodecylamine (DDA). Specifically, it consists of the following manufacturing procedures.

［製造手順］
（１）CuCl、InCl3、Ga(acac)3をSe粉末と共に室温状態でＤＤＡと混合し原料液とする（図１（ａ））。
（２）次に、原料液を２５０℃まで段階的に昇温する。具体的には、次の５工程を経て段階的に昇温する（図１（ｂ））。
第１工程：室温から１００℃まで０．５時間かけて昇温。
第２（前期）工程：１００℃から１５０℃まで０．５時間かけて昇温。
第２（後期）工程：１５０℃から２００℃まで１時間かけて昇温。
第３（前期）工程：２００℃から２２５℃まで１時間かけて昇温。
第３（後期）工程：２２５℃から２５０℃まで１時間かけて昇温。
以上の昇温工程により、ナノ粒子がＤＤＡ中に分散したナノ粒子分散液が得られる（図１（ｃ））。 [Manufacturing procedure]
(1) CuCl, InCl 3 and Ga (acac) 3 are mixed with DDA together with Se powder at room temperature to obtain a raw material liquid (FIG. 1 (a)).
(2) Next, the temperature of the raw material liquid is raised stepwise to 250 ° C. Specifically, the temperature is raised stepwise through the following five steps (FIG. 1B).
First step: Raise temperature from room temperature to 100 ° C. over 0.5 hours.
Second (first term) step: Raise the temperature from 100 ° C to 150 ° C over 0.5 hours.
2nd (late stage) process: It heated up from 150 degreeC to 200 degreeC over 1 hour.
Third (first term) step: The temperature was raised from 200 ° C. to 225 ° C. over 1 hour.
3rd (late stage) process: It heats up from 225 degreeC to 250 degreeC over 1 hour.
Through the above temperature raising step, a nanoparticle dispersion liquid in which nanoparticles are dispersed in DDA is obtained (FIG. 1C).

（３）得られたナノ粒子分散液からナノ粒子を取り出してメタノールで洗い、トルエンに分散させる。トルエン分散液は、印刷法により化合物太陽電池の光吸収層を作製するためのインクとして利用することができる。なお、製造例１での、収率は９０％以上であった。 (3) Nanoparticles are taken out from the obtained nanoparticle dispersion, washed with methanol, and dispersed in toluene. The toluene dispersion can be used as an ink for producing a light absorption layer of a compound solar cell by a printing method. The yield in Production Example 1 was 90% or more.

図２は、第１工程、第２（前期）工程、第２（後期）工程、第３（前期）工程の各工程における走査型電子顕微鏡写真（ＳＥＭ写真）であり（図２の（ａ）〜（ｄ））、図３は第３（後期）工程におけるＳＥＭ写真である。これらの図から分かるように、第１工程では比較的大きなプレート状の粒子が観察された。第２（前期）工程では、ところどころプレート状の粒子がみられるものの球状の微小粒子が多く観察された。また、第２（後期）工程及び第３（前期）工程では、ほぼ全てが球状の微小粒子であり、プレート状の粒子はわずかしか存在しなかった。第３（後期）工程では、粒径が20 nm以下の球状の均一な微小粒子が観察された。   FIG. 2 is a scanning electron micrograph (SEM photograph) in each step of the first step, the second (first term) step, the second (late term) step, and the third (first term) step ((a) of FIG. 2). (D)) and FIG. 3 are SEM photographs in the third (late stage) process. As can be seen from these figures, relatively large plate-like particles were observed in the first step. In the second (first term) process, many spherical fine particles were observed although some plate-like particles were observed. In the second (late) step and the third (previous) step, almost all were spherical fine particles, and there were only a few plate-like particles. In the third (late stage) step, spherical uniform fine particles having a particle size of 20 nm or less were observed.

図４に、図２の（ａ）〜（ｄ）及び図３に示す粒子のＸＲＤ結果を示し、図５に、図３に示す粒子のＸＲＤ結果とJCPDS（Joint Committee for Powder Diffraction Standards）カードから参照したＣＩＧＳのＸＲＤパターンを示す。これらの図から、第３（前期）工程までに得られた粒子は、CuInGaSe、CuInSe、CuSe、Se単体の混合物であったが、第３（後期）工程において得られた粒子はほぼ全てがCuInGaSeであることが分かった。   FIG. 4 shows the XRD results of the particles shown in FIGS. 2A to 2D and FIG. 3, and FIG. 5 shows the XRD results of the particles shown in FIG. 3 and the JCPDS (Joint Committee for Powder Diffraction Standards) card. The XRD pattern of the referred CIGS is shown. From these figures, the particles obtained up to the third (early) step were a mixture of CuInGaSe, CuInSe, CuSe, and Se, but almost all the particles obtained in the third (late) step were CuInGaSe. It turns out that.

下記の表１は、原料元素の配合比率を変えてナノ粒子を合成したときの該ナノ粒子の組成比の測定値及びバンドギャップの値を示したものである。表１に示すように、製造例１の方法では、原料元素の配合比率を変えることにより、CuInGaSe系ナノ粒子の組成比やバンドギャップを制御できることが分かる。
Table 1 below shows measured values of the composition ratio of the nanoparticles and band gap values when the nanoparticles were synthesized by changing the mixing ratio of the raw material elements. As shown in Table 1, it can be seen that in the method of Production Example 1, the composition ratio and band gap of CuInGaSe-based nanoparticles can be controlled by changing the blending ratio of the raw material elements.

［製造例２］
原料金属と溶媒との反応は２００℃付近で進行することから、第２（後期）工程の昇温速度が、得られるナノ粒子の大きさや形状に及ぼす影響を調べた。第２（後期）工程以外の工程の昇温速度は製造例１と同じである。また、この製造例２では、第３工程により２５０℃まで加熱した後、２５０℃の状態を４時間保持してから得られたナノ粒子について調べた。
［実験１］
実験１では、第２（後期）工程の昇温速度を約0.7℃/minとしてナノ粒子を合成した。得られたナノ粒子のＳＥＭ写真を図６（ａ）に、ＴＧ解析の結果を図６（ｂ）に示す。図６（ａ）から、ナノ粒子は比較的大きく、板状をしていることが分かる。また、図６（ｂ）に示すように、ＴＧ解析からは不純物量が10%程度であることが分かった。 [Production Example 2]
Since the reaction between the raw material metal and the solvent proceeds at around 200 ° C., the influence of the temperature increase rate in the second (late stage) step on the size and shape of the obtained nanoparticles was investigated. The rate of temperature increase in the processes other than the second (late stage) process is the same as in Production Example 1. In Production Example 2, after heating to 250 ° C. in the third step, the nanoparticles obtained after maintaining the state at 250 ° C. for 4 hours were examined.
[Experiment 1]
In Experiment 1, nanoparticles were synthesized at a rate of temperature increase in the second (late stage) step of about 0.7 ° C./min. The SEM photograph of the obtained nanoparticles is shown in FIG. 6 (a), and the result of TG analysis is shown in FIG. 6 (b). FIG. 6A shows that the nanoparticles are relatively large and have a plate shape. Further, as shown in FIG. 6B, it was found from the TG analysis that the amount of impurities is about 10%.

［実験２］
実験２は製造例１とほぼ同じ手順でナノ粒子を合成した。すなわち、第２（後期）工程の昇温速度を約1℃/minとしてナノ粒子を合成した。得られたナノ粒子のＳＥＭ写真を図７（ａ）に、ＴＧ解析の結果を図７（ｂ）に示す。図７（ａ）から、ナノ粒子は、粒径が20-25 nm程度の、均一な（単分散の）球状粒子であることが分かる。また、ＴＧ解析から不純物量は10%程度であった。
［実験３］
実験３では、第２（後期）工程の昇温速度を約2.5℃/minとしてナノ粒子を合成した。得られたナノ粒子のＳＥＭ写真を図８（ａ）に、ＴＧ解析の結果を図８（ｂ）に示す。図８（ａ）から、ナノ粒子は、粒径が15-20 nm程度の、均一な（単分散の）球状粒子であることが分かった。また、図８（ｂ）のＴＧ解析の結果から不純物量は10%程度であった。 [Experiment 2]
In Experiment 2, nanoparticles were synthesized by almost the same procedure as in Production Example 1. That is, the nanoparticles were synthesized at a rate of temperature increase in the second (late stage) step of about 1 ° C./min. The SEM photograph of the obtained nanoparticles is shown in FIG. 7 (a), and the result of TG analysis is shown in FIG. 7 (b). FIG. 7A shows that the nanoparticles are uniform (monodispersed) spherical particles having a particle size of about 20-25 nm. Moreover, the amount of impurities was about 10% from TG analysis.
[Experiment 3]
In Experiment 3, nanoparticles were synthesized at a heating rate of the second (late stage) step of about 2.5 ° C./min. The SEM photograph of the obtained nanoparticles is shown in FIG. 8 (a), and the result of TG analysis is shown in FIG. 8 (b). FIG. 8A shows that the nanoparticles are uniform (monodispersed) spherical particles having a particle size of about 15-20 nm. Moreover, the impurity amount was about 10% from the result of TG analysis of FIG.8 (b).

図９に、実験１〜３で得られたナノ粒子のＸＲＤ解析の結果を示す。図９から分かるように、実験１〜３で得られたナノ粒子は、ＸＲＤパターンにショルダが現れ、不純物ピークが観察された。特に実験１のナノ粒子のＸＲＤパターンには比較的大きなショルダが現れた。以上の結果から、実験１のように１５０℃から２００℃までゆっくりと昇温した場合は、実験１よりも昇温速度が速い実験２及び実験３の場合に比べて、得られるナノ粒子の粒径が大きく且つ板状になることが分かった。また、ナノ粒子の純度の点でも昇温速度が速いほうが優れていることが分かった。このことから、第２（後期）工程の昇温速度は、ナノ粒子の形状や粒径、粒径分布、純度に影響を及ぼすと思われた。   FIG. 9 shows the results of XRD analysis of the nanoparticles obtained in Experiments 1-3. As can be seen from FIG. 9, in the nanoparticles obtained in Experiments 1 to 3, a shoulder appeared in the XRD pattern, and an impurity peak was observed. In particular, a relatively large shoulder appeared in the XRD pattern of the nanoparticles in Experiment 1. From the above results, when the temperature is slowly raised from 150 ° C. to 200 ° C. as in Experiment 1, the resulting nanoparticles particles are faster than those in Experiment 2 and Experiment 3 where the heating rate is faster than in Experiment 1 It was found that the diameter was large and a plate shape was obtained. Moreover, it turned out that the one where a temperature increase rate is quick is excellent also in the point of the purity of a nanoparticle. From this, it was considered that the rate of temperature increase in the second (late) step affects the shape, particle size, particle size distribution, and purity of the nanoparticles.

＜溶媒の検討＞
溶媒による違いを調べるために、ＤＤＡに代えてペンタデシルアミン（C15H33N、（ＰＤＡ））を用いて、実験２と同じ工程でナノ粒子を合成した。その結果、得られたナノ粒子の粒径は25-30 nm程度であり、ＤＤＡを用いた時に比べると粒径が大きいことが分かった。また、粒径の分布はＤＤＡに比べると不均一であった。さらに、ＴＧＡ解析の結果から、有機成分の不純物の量は10%程度であり、ＤＤＡとほとんど差はないことが分かった。
一方、ＸＲＤ解析の結果から、ＰＤＡを用いた場合に得られる微粒子は、CIGS単相でなく無機系の不純物が含まれていると考えられた。図１０に、溶媒としてＤＤＡを用いた場合、ＰＤＡを用いた場合のそれぞれにおいて得られたナノ粒子のＳＥＭ写真を示す。また、図１１に、ＰＤＡを用いたときに得られたナノ粒子のＴＧＡ解析の結果及びＸＲＤ解析の結果を示す。 <Study of solvent>
In order to investigate the difference depending on the solvent, nanoparticles were synthesized in the same process as in Experiment 2 using pentadecylamine (C 15 H 33 N, (PDA)) instead of DDA. As a result, it was found that the obtained nanoparticles had a particle size of about 25-30 nm, which was larger than when DDA was used. Also, the particle size distribution was non-uniform compared to DDA. Furthermore, from the results of TGA analysis, it was found that the amount of organic component impurities is about 10%, which is almost the same as DDA.
On the other hand, from the results of XRD analysis, it was considered that the fine particles obtained when PDA was used contained inorganic impurities, not a CIGS single phase. FIG. 10 shows SEM photographs of nanoparticles obtained in the case of using DDA as a solvent and in the case of using PDA. FIG. 11 shows the result of TGA analysis and the result of XRD analysis of nanoparticles obtained using PDA.

Claims (6)

周期律表の第I族金属化合物、第III族金属化合物、及び第VI族金属の単体をアミン系溶媒中に入れて混合し、加熱して、前記第I族金属化合物及び前記第III族金属化合物と、前記第VI族金属の単体を反応させることによりカルコパイライトナノ粒子を製造する方法であって、
加熱する工程が、
第１昇温速度で室温から１００℃まで昇温する第１昇温工程と、
前記第１昇温速度よりも遅い第２昇温速度で１００℃から２００℃まで昇温する第２昇温工程と
を有することを特徴とするカルコパイライトナノ粒子の製造方法。 The Group I metal compound, Group III metal compound, and Group VI metal in the periodic table are mixed in an amine solvent and heated to heat the Group I metal compound and Group III metal. A method of producing chalcopyrite nanoparticles by reacting a compound and a simple substance of the Group VI metal,
The heating process is
A first temperature raising step for raising the temperature from room temperature to 100 ° C. at a first temperature raising rate;
And a second temperature raising step of raising the temperature from 100 ° C. to 200 ° C. at a second temperature raising rate that is slower than the first temperature raising rate. 前記第２昇温工程が、１００℃から１５０℃まで昇温する前期工程と、該前期工程よりも遅い昇温速度で１５０℃から２００℃まで昇温する後期工程から成ることを特徴とする請求項１に記載のカルコパイライトナノ粒子の製造方法。   The second temperature raising step is composed of a first step for raising the temperature from 100 ° C to 150 ° C and a second step for raising the temperature from 150 ° C to 200 ° C at a rate of temperature rise slower than the first step. Item 2. A method for producing chalcopyrite nanoparticles according to Item 1. 加熱する工程が、さらに、前記第２昇温速度よりも遅い第３昇温速度で２００℃から２５０℃まで昇温する第３昇温工程を備えることを特徴とする請求項１又は２に記載のカルコパイライトナノ粒子の製造方法。   The heating step further comprises a third temperature raising step for raising the temperature from 200 ° C. to 250 ° C. at a third temperature raising rate that is slower than the second temperature raising rate. Method for producing chalcopyrite nanoparticles. 前記第I族金属化合物が銅塩、前記第III族金属化合物がインジウム塩又は／及びガリウム塩、前記第VI族金属がセレンであることを特徴とする請求項１〜３のいずれかに記載のカルコパイライトナノ粒子の製造方法。   The group I metal compound is a copper salt, the group III metal compound is an indium salt and / or a gallium salt, and the group VI metal is selenium. A method for producing chalcopyrite nanoparticles. アミン系溶媒が、ドデシル・アミンであることを特徴とする請求項１〜４のいずれかに記載のカルコパイライトナノ粒子の製造方法。   The method for producing chalcopyrite nanoparticles according to any one of claims 1 to 4, wherein the amine solvent is dodecylamine. 前記第１昇温速度が2.5℃/min〜3.5℃/minであり、前記第２昇温速度が0.8℃/min〜2.5℃/minであることを特徴とする請求項１〜５のいずれかに記載のカルコパイライトナノ粒子の製造方法。   The first temperature increase rate is 2.5 ° C / min to 3.5 ° C / min, and the second temperature increase rate is 0.8 ° C / min to 2.5 ° C / min. The manufacturing method of the chalcopyrite nanoparticle described in 1.
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