JP2015174910A - Semiconductor particle paste and photoelectric conversion device - Google Patents

Semiconductor particle paste and photoelectric conversion device Download PDF

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JP2015174910A
JP2015174910A JP2014052029A JP2014052029A JP2015174910A JP 2015174910 A JP2015174910 A JP 2015174910A JP 2014052029 A JP2014052029 A JP 2014052029A JP 2014052029 A JP2014052029 A JP 2014052029A JP 2015174910 A JP2015174910 A JP 2015174910A
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徹 仲山
Toru Nakayama
徹 仲山
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Kyocera Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a semiconductor particle paste in which semiconductor nanocrystal becoming quantum dot can be integrated at high density, and a photoelectric conversion device to which the semiconductor particle paste is applied.SOLUTION: The semiconductor particle paste is provided in which luminescent nanocrystal having a maximum diameter of 20 nm or less is dispersed in solution of an organic molecule 15a containing a metal complex 14. In this case, it is preferred that: the metal complex is one kind of in vivo complex selected from a group of hemoglobin, myoglobin, chlorophyll, bleomycin, vitamin B, molybutoten hemocyanin, ferredoxin; or the metal complex includes one kind of metal ion selected from a group of Na, K, Mg, Ca, Al, Mn, Co, Fe, Cu, Zn, Mo, Pd and Pt and one kind of ligand selected from a group of CO, NO, NH, RNH, RCOO, RO, ROH, NH, PO, ROPOand (RO)PO.

Description

本発明は、半導体粒子ペーストおよび光電変換装置に関する。   The present invention relates to a semiconductor particle paste and a photoelectric conversion device.

近年、太陽電池や半導体レーザなどの光電変換装置は、その変換効率を高めるために量子ドットを利用することが提案されている（例えば、特許文献１を参照）。   In recent years, photoelectric conversion devices such as solar cells and semiconductor lasers have been proposed to use quantum dots in order to increase the conversion efficiency (see, for example, Patent Document 1).

この場合に適用される量子ドットとしては、サイズが約２０ｎｍ程度の半導体材料を主成分とするナノ結晶となるが、従来より用いられているナノ結晶には、元々、形状やサイズにばらつきがあり、ペースト化してもナノ結晶を高密度に集積させることができず、高効率の光電変換装置を得ることができないという問題があった。   The quantum dots applied in this case are nanocrystals whose main component is a semiconductor material having a size of about 20 nm. However, the conventional nanocrystals have variations in shape and size. However, there is a problem in that nanocrystals cannot be accumulated at high density even when pasted, and a highly efficient photoelectric conversion device cannot be obtained.

特開２００６−１１４８１５号公報JP 2006-114815 A

本発明は上記課題に鑑みてなされたものであり、量子ドットとなるナノ結晶を高密度に集積させることのできる半導体粒子ペーストと、それを適用した光電変換装置を提供することを目的とする。   This invention is made | formed in view of the said subject, and it aims at providing the semiconductor particle paste which can integrate the nanocrystal used as a quantum dot with high density, and a photoelectric conversion apparatus using the same.

本発明の半導体粒子ペーストは、金属錯体を含む有機分子の溶液中に、最大径が１〜２０ｎｍで、発光性を示すナノ結晶を分散させていることを特徴とする。   The semiconductor particle paste of the present invention is characterized in that nanocrystals having a maximum diameter of 1 to 20 nm and exhibiting luminescent properties are dispersed in a solution of an organic molecule containing a metal complex.

本発明の光電変換装置は、半導体基板の主面上に、上記のナノ結晶の集積膜を有していることを特徴とする。   The photoelectric conversion device of the present invention is characterized by having the above-mentioned nanocrystal integrated film on the main surface of a semiconductor substrate.

本発明によれば、量子ドットとなる半導体性のナノ結晶を高密度に集積させることのできる半導体粒子ペーストと、それを適用した光電変換装置を得ることできる。   ADVANTAGE OF THE INVENTION According to this invention, the semiconductor particle paste which can integrate the semiconducting nanocrystal used as a quantum dot with high density, and a photoelectric conversion apparatus using the same can be obtained.

本発明の光電変換装置の一実施形態を示す断面模式図である。It is a cross-sectional schematic diagram which shows one Embodiment of the photoelectric conversion apparatus of this invention. 本発明の半導体粒子ペーストの製法の一例を示す断面模式図である。It is a cross-sectional schematic diagram which shows an example of the manufacturing method of the semiconductor particle paste of this invention.

本実施形態の半導体粒子ペーストは、金属錯体を含む有機分子の溶液中に、最大径が１〜２０ｎｍで、発光性を示すナノ結晶を分散させているものである。   The semiconductor particle paste of the present embodiment is one in which nanocrystals having a maximum diameter of 1 to 20 nm and exhibiting luminescent properties are dispersed in a solution of organic molecules containing a metal complex.

この半導体粒子ペーストは、半導体材料を主成分とするナノ結晶を有機分子中に含有させたものであるため、半導体粒子ペーストをそのまま半導体基板の表面に塗布した際にも、ペースト中に含まれるナノ結晶は、有機分子を介して分散された状態であることから流動性の高いものとなる。   Since this semiconductor particle paste contains nanocrystals mainly composed of a semiconductor material in organic molecules, even when the semiconductor particle paste is directly applied to the surface of a semiconductor substrate, the nanoparticle contained in the paste is included. Since the crystal is dispersed through organic molecules, the crystal has high fluidity.

また、ナノ結晶は、溶液中において、金属錯体が近接した状態で存在しているため、有
機分子よりもイオン性の強い無機物である金属錯体と結合しやすくなっている。このためナノ結晶は優先的に金属錯体を介して結合するようになり、ナノ結晶が集積された際には両者の結合間隔を狭くすることができる。その結果、ナノ結晶による密度の高い集積膜を形成することができ、変換効率の高い光電変換装置を得ることができる。 In addition, since nanocrystals exist in a solution in a state where the metal complexes are close to each other, the nanocrystals are easily bonded to a metal complex that is an inorganic substance having stronger ionicity than organic molecules. Therefore, the nanocrystals are preferentially bonded via the metal complex, and when the nanocrystals are integrated, the bonding interval between the two can be narrowed. As a result, an integrated film with a high density of nanocrystals can be formed, and a photoelectric conversion device with high conversion efficiency can be obtained.

この場合、ナノ結晶の最大径が１〜２０ｎｍとなっていることで、同じ組成でサイズの大きい半導体材料の粒子に比較して高いエネルギーギャップ（Ｅｇ）を有するものとなっているため、このナノ結晶に可視光（波長：４００〜１０００ｎｍ）を照射すると、ナノ結晶は照射した光のエネルギーによってキャリアの励起と緩和（降下）を繰り返すものとなり発光性の高いものとなる。この場合、発光性の評価はフォトルミネッセンス分析により行う。   In this case, since the maximum diameter of the nanocrystal is 1 to 20 nm, the nanocrystal has a high energy gap (Eg) compared to particles of a semiconductor material having the same composition and a large size. When the crystal is irradiated with visible light (wavelength: 400 to 1000 nm), the nanocrystal repeats excitation and relaxation (lowering) of the carrier by the energy of the irradiated light and becomes highly luminescent. In this case, evaluation of luminescent property is performed by photoluminescence analysis.

これに対し、ナノ結晶の最大径が２０ｎｍを超えるものが含まれているような場合には、ナノ結晶を集積させた膜の密度を高めることが困難になるとともに、ナノ結晶自体も発光性の弱いものとなってしまうことから光電変換効率も低くなってしまう。   On the other hand, when the maximum diameter of the nanocrystal exceeds 20 nm, it is difficult to increase the density of the film in which the nanocrystal is integrated, and the nanocrystal itself is also luminescent. Since it becomes weak, photoelectric conversion efficiency will also become low.

一方、ナノ結晶の最大径が１ｎｍよりも小さい場合には、発光性をほとんど示さなくなり、量子ドットとしての機能を発揮できないものとなる。   On the other hand, when the maximum diameter of the nanocrystal is smaller than 1 nm, light emission is hardly exhibited and the function as a quantum dot cannot be exhibited.

この半導体粒子ペーストを構成するナノ結晶のサイズは、例えば、中間バンド方式に代表される量子ドットとして好適なものとなるが、この場合、密度の高い集積膜を形成できるという理由から、ナノ結晶の形状としては、球状体が好ましいものとなるが、これ以外に立方体や柱状体など等方的な寸法を有する形状であっても良い。なお、ナノ結晶が球状体である場合には、真球度は０．８０以上１．００以下であることがより望ましい。   The size of the nanocrystals constituting this semiconductor particle paste is suitable, for example, as a quantum dot typified by the intermediate band method. In this case, because of the fact that a dense integrated film can be formed, As the shape, a spherical body is preferable, but other than this, a shape having an isotropic dimension such as a cube or a columnar body may be used. When the nanocrystal is a spherical body, the sphericity is more preferably 0.80 or more and 1.00 or less.

このような形状のナノ結晶を含む半導体粒子ペーストを用いると、集積膜に占めるナノ結晶の割合を集積膜の断面観察から得られる面積比で７０％以上にすることができる。   When a semiconductor particle paste containing nanocrystals having such a shape is used, the ratio of nanocrystals in the integrated film can be made 70% or more in terms of the area ratio obtained from cross-sectional observation of the integrated film.

また、上記のような形状を有するナノ結晶であれば、半導体粒子ペーストには最大径の異なるナノ結晶が含まれていても良い。半導体粒子ペースト中に最大径の異なるナノ結晶を含ませるようにすると、大きいサイズのナノ結晶の隙間に小さいサイズのナノ結晶を充填できることからナノ結晶の充填率をさらに高めることができ、導電率の高い光電変換装置を形成することができる。この場合、最大径の範囲としては、ナノ結晶が強い発光性を示すものになるという点で１〜２０ｎｍ、特に、５〜１０ｎｍであることが望ましい。   Moreover, as long as it is a nanocrystal which has the above shapes, the semiconductor particle paste may contain nanocrystals having different maximum diameters. By including nanocrystals with different maximum diameters in the semiconductor particle paste, it is possible to fill the gaps between the large sized nanocrystals with small sized nanocrystals, which can further increase the filling rate of the nanocrystals and increase the conductivity. A high photoelectric conversion device can be formed. In this case, the range of the maximum diameter is preferably 1 to 20 nm, particularly 5 to 10 nm in that the nanocrystal exhibits strong light emission.

ここで、最大径とは、個々のナノ結晶における最長径のことを言い、例えば、透過電子顕微鏡により撮影された写真から求められる最大の長さに相当する。ナノ結晶の真球度は、例えば、ベックマン・コールター・ラピッドＶＵＥ画像解析装置（Ｂｅｃｋｍａｎ Ｃｏｕｌｔｅｒ Ｒａｐｉｄ ＶＵＥ Ｉｍａｇｅ Ａｎａｌｙｚｅｒ）バージョン２．０６（ベックマン・コールター社、フロリダ州マイアミ）を用いて決定することができる。具体的には、Ｒａｐｉｄ ＶＵＥが、連続階調（グレースケール）形式の画像を撮影し、これをサンプリングおよび量子化の処理を経てデジタル形式に変換する。システムソフトウェアが、画像内の繊維状、桿状または球状の粒子の同定と測定とを行う。Ｄａ／Ｄｐ（Ｄａ＝√（４Ａ／π）；Ｄｐ＝Ｐ／π；Ａ＝ピクセル面積；Ｐ＝ピクセル周長）として計算される粒子の真球度は、ゼロから１の間の値であり、１が真球を示すものとなる。   Here, the maximum diameter means the longest diameter of each nanocrystal, and corresponds to the maximum length obtained from a photograph taken with a transmission electron microscope, for example. The sphericity of the nanocrystal can be determined using, for example, a Beckman Coulter Rapid VUE Image Analyzer version 2.06 (Beckman Coulter, Miami, FL). Specifically, the Rapid VUE takes an image in a continuous tone (grayscale) format and converts it into a digital format through sampling and quantization processes. System software identifies and measures the fibrous, bowl-like or spherical particles in the image. The sphericity of a particle calculated as Da / Dp (Da = √ (4A / π); Dp = P / π; A = pixel area; P = pixel circumference) is a value between zero and one 1 indicates a true sphere.

本実施形態の半導体粒子ペーストに含ませる金属錯体としては、含まれる金属の安定度定数が高いという点で、ヘモグロビン、ミオグロビン、クロロフィル、ブレオマイシン、ビタミンＢ１２、モリブトテンヘモシニアン、フェレドキシンの群から選ばれる１種の生体内錯体が好適なものとなるが、他に、Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ａｌ、Ｍｎ、Ｃｏ、Ｆｅ
、Ｃｕ、Ｚｎ、Ｍｏ、ＰｄおよびＰｔの群から選ばれる少なくとも１種の金属イオンと、ＣＯ３ ２−、ＮＯ３ −、ＮＨ３、ＲＮＨ２、ＲＣＯＯ−、ＲＯ−、ＲＯＨ、Ｎ２Ｈ４、ＰＯ４ ３−、ＲＯＰＯ３ ２−、（ＲＯ）２ＰＯ２−の群から選ばれる１種の配位子とを含む金属錯体でも良く、これらの金属錯体はいずれもこれらが金属の酸化物や炭酸化合物あるいは少なくとも上記のマイナスイオンを含む形態に変成されて中間層となり同様の効果を発揮できる。 The metal complex contained in the semiconductor particle paste of the present embodiment is from the group of hemoglobin, myoglobin, chlorophyll, bleomycin, vitamin B 12 , molybtoten hemocyanin, ferredoxin in that the stability constant of the metal contained is high. One kind of in vivo complex selected is suitable, but other than that, Na, K, Mg, Ca, Al, Mn, Co, Fe
, Cu, Zn, Mo, Pd and Pt, at least one metal ion selected from the group consisting of CO 3 2− , NO 3 − , NH 3 , RNH 2 , RCOO − , RO − , ROH, N 2 H 4 , PO 4 3− , ROPO 3 2− , (RO) 2 PO 2− may be a metal complex containing one kind of ligand, and these metal complexes are all oxides of these metals. It can be transformed to a form containing carbonic acid compound or at least the above-mentioned negative ions to form an intermediate layer and exhibit the same effect.

半導体粒子ペーストについては、ナノ結晶が流動しやすいチキソトロピー性の粘度特性を有するものであるのが良く、例えば、室温（２５℃）において、１ｍＰａ・ｓ以上５０ｍＰａ・ｓ以下の粘度を示すものが望ましい。これにより、例えば、９００ｃｍ２以上の大面積の集積膜を形成する場合でも４隅と中央部との厚み差を約０．１μｍの差で形成することができる。 The semiconductor particle paste should have a thixotropic viscosity characteristic in which nanocrystals are easy to flow. For example, a paste exhibiting a viscosity of 1 mPa · s to 50 mPa · s at room temperature (25 ° C.) is desirable. . Thereby, for example, even when an integrated film having a large area of 900 cm 2 or more is formed, the thickness difference between the four corners and the central portion can be formed with a difference of about 0.1 μm.

また、半導体粒子ペーストがこのような粘度特性を有するようなものであると、有機分子がナノ結晶を拘束した状態を長期間維持できることから、保存性が良く、かつ長期間にわたって高い充填性の集積膜を形成することができる。   In addition, if the semiconductor particle paste has such a viscosity characteristic, the organic molecules can maintain the state in which the nanocrystals are constrained to the nanocrystals for a long period of time. A film can be formed.

この場合、半導体粒子ペーストを構成する有機分子としては、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセンなどの炭素数２〜２０のα−オレフィンから選ばれる少なくとも１種が望ましい。上記した有機分子は分子量も小さいため、有機分子同士の絡みも少ないことから、室温（２５℃）において、１ｍＰａ・ｓ以上５０ｍＰａ・ｓ以下の範囲の粘度特性を長期間維持することができる。   In this case, the organic molecules constituting the semiconductor particle paste include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, At least one selected from α-olefins having 2 to 20 carbon atoms such as 1-octadecene and 1-eicosene is desirable. Since the above-mentioned organic molecules have a small molecular weight, and there is little entanglement between the organic molecules, the viscosity characteristics in the range of 1 mPa · s to 50 mPa · s can be maintained for a long time at room temperature (25 ° C.).

このような半導体粒子ペーストを構成するナノ結晶としては、半導体材料を主成分とするものからなり、そのエネルギーギャップ（Ｅｇ）は用いる材料によって異なるが、０．１５〜２．５０ｅｖを有するものが好適である。具体的な量子ドット５ａの材料としては、ゲルマニウム（Ｇｅ）、シリコン（Ｓｉ）、ガリウム（Ｇａ）、インジウム（Ｉｎ）、ヒ素（Ａｓ）、アンチモン（Ｓｂ）、銅（Ｃｕ）、鉄（Ｆｅ）、硫黄（Ｓ）、鉛（Ｐｂ）、テルル（Ｔｅ）およびセレン（Ｓｅ）から選ばれるいずれか１種またはこれらの化合物半導体を用いることが望ましい。   Nanocrystals constituting such a semiconductor particle paste are composed mainly of a semiconductor material, and the energy gap (Eg) varies depending on the material used, but those having 0.15 to 2.50 ev are suitable. It is. Specific materials for the quantum dots 5a include germanium (Ge), silicon (Si), gallium (Ga), indium (In), arsenic (As), antimony (Sb), copper (Cu), iron (Fe). It is desirable to use any one selected from sulfur (S), lead (Pb), tellurium (Te) and selenium (Se) or a compound semiconductor thereof.

図１は、本発明の光電変換装置の一実施形態を示す断面模式図である。本実施形態の光電変換装置は、半導体基板１の主面上に、上記の半導体粒子ペーストに含まれるナノ結晶３が連結された集積膜５を有するものである。本実施形態の光電変換装置によれば、上述したサイズを有する半導体性のナノ結晶３に金属錯体が付与されて形成されるものであるため、ナノ結晶３は加熱後には金属錯体に由来する無機配位子４を介して連結された状態になることから、分子量が高くなると立体障害などにより体積が大きくなる有機分子などに比較して量子ドットとなるナノ結晶３の集積膜５を高密度なものにできる。これにより高い光電変換効率を有する光電変換装置を得ることができる。   FIG. 1 is a schematic cross-sectional view showing one embodiment of the photoelectric conversion device of the present invention. The photoelectric conversion device of the present embodiment has an integrated film 5 on a main surface of a semiconductor substrate 1 to which nanocrystals 3 contained in the semiconductor particle paste are connected. According to the photoelectric conversion device of the present embodiment, since the metal complex is formed on the semiconducting nanocrystal 3 having the above-described size, the nanocrystal 3 is inorganic derived from the metal complex after heating. Since it is connected via the ligand 4, the integrated film 5 of the nanocrystals 3 serving as quantum dots is formed in a higher density than an organic molecule whose volume increases due to steric hindrance when the molecular weight increases. Can be a thing. Thereby, a photoelectric conversion device having high photoelectric conversion efficiency can be obtained.

図１には、半導体基板１と、無機配位子４を含むナノ結晶３の集積膜５との２層構造を示したにすぎないが、この集積膜５は多層化されていても良いし、また、この集積膜５の上側にも半導体基板１（もしくは半導体の膜）が設けられていてもよい。この場合、集積膜５の上層および下層に設けた半導体基板１をｐ型またはｎ型として機能するようにすると、ナノ結晶３の集積膜５にさらに２つの半導体基板１による光電変換が加わるため、光電変換効率をさらに向上させることができる。   FIG. 1 only shows a two-layer structure of the semiconductor substrate 1 and the integrated film 5 of the nanocrystal 3 containing the inorganic ligand 4, but the integrated film 5 may be multilayered. Also, the semiconductor substrate 1 (or a semiconductor film) may be provided on the upper side of the integrated film 5. In this case, if the semiconductor substrate 1 provided in the upper layer and the lower layer of the integrated film 5 is made to function as p-type or n-type, photoelectric conversion by the two semiconductor substrates 1 is further added to the integrated film 5 of the nanocrystal 3. Photoelectric conversion efficiency can be further improved.

次に、本実施形態の半導体粒子ペーストおよび光電変換装置を製造する方法について、図２を基に説明する。本実施形態の半導体粒子ペーストは、半導体素原料粒子１１を、硝
酸とフッ酸とを混合した酸性溶液１３とこの溶液よりも比重の低い有機分子１５ａの溶液１５（以下、有機分子溶液１５という。）の混合溶液中に分散させた後に、その混合溶液に超音波振動を与えることにより調製される。 Next, a method for producing the semiconductor particle paste and the photoelectric conversion device of the present embodiment will be described with reference to FIG. In the semiconductor particle paste of this embodiment, the semiconductor raw material particles 11 are referred to as an acidic solution 13 in which nitric acid and hydrofluoric acid are mixed, and a solution 15 of organic molecules 15a having a specific gravity lower than this solution (hereinafter referred to as organic molecule solution 15). ) After being dispersed in the mixed solution, and then applying ultrasonic vibration to the mixed solution.

半導体素原料粒子１１を硝酸とフッ酸とを混合した酸性溶液１３（以下、単に、酸性溶液１３という場合がある。）中に分散させて、超音波振動を与えると、溶解反応により半導体素原料粒子１１が熱融解し、微少サイズ（最大径が１０ｎｍ以下）の粒子１１ａが生成する。後に、この粒子１１ａが結晶化して発光性を有するナノ結晶３となる。生成した粒子１１ａはサイズが小さいために、比重の大きい酸性溶液１３中において液面付近まで浮上してくる。   When the semiconductor raw material particles 11 are dispersed in an acidic solution 13 in which nitric acid and hydrofluoric acid are mixed (hereinafter sometimes simply referred to as acidic solution 13) and subjected to ultrasonic vibration, the semiconductor raw material is dissolved by a dissolution reaction. The particles 11 are melted by heat to generate particles 11a having a very small size (maximum diameter is 10 nm or less). Later, the particles 11a are crystallized to form a nanocrystal 3 having luminescence. Since the generated particles 11a are small in size, they float up to the vicinity of the liquid surface in the acidic solution 13 having a large specific gravity.

この工程では、硝酸とフッ酸との酸性溶液１３とともに、この酸性溶液１３よりも比重の低い有機分子溶液１５に金属錯体１４を含ませており、また、この系においては酸性溶液１３の上側に有機分子溶液１５が分離した状態で存在しているため、酸性溶液１３の液面付近まで浮上した粒子１１ａ（またはナノ結晶３）は有機分子溶液１５中に存在する金属錯体１４および有機分子１５ａと結合し、有機分子溶液１５の層に分散した状態となる。   In this process, together with the acidic solution 13 of nitric acid and hydrofluoric acid, a metal complex 14 is included in an organic molecular solution 15 having a specific gravity lower than that of the acidic solution 13, and in this system, on the upper side of the acidic solution 13. Since the organic molecular solution 15 exists in a separated state, the particles 11a (or nanocrystals 3) that have floated to the vicinity of the liquid surface of the acidic solution 13 are separated from the metal complex 14 and the organic molecules 15a that exist in the organic molecular solution 15. They are bonded and dispersed in the layer of the organic molecule solution 15.

この方法によれば、半導体素原料粒子１１から熱融解によって微少サイズの粒子１１ａを生成させる際に、硝酸とフッ酸とを含み、比重の重い酸性溶液１３中に分散するようにしているため、生成した微少サイズの粒子１１ａは沈降しにくく、また、粒子１１ａの周囲が高い比重を有する媒体であることから生成した粒子１１ａは周囲から等方的な圧力を受けることになる。その結果、熱融解して生成した粒子１１ａは冷却されてナノ結晶３になる間、酸性溶液１３中に浮遊した状態で存在することから、生成するナノ結晶３のほとんどが等方的な形状となるため、最大径が２０ｎｍに近いサイズでも、真球度の高いナノ結晶３を多くの割合で含むものにできる。この場合、粒子１１ａの最大径は酸性溶液中に含まれる硝酸（ＮＯ３ −）およびフッ酸（Ｆ−）の濃度によって調整できる。 According to this method, when the fine particles 11a are generated from the semiconductor raw material particles 11 by heat melting, the particles 11a contain nitric acid and hydrofluoric acid and are dispersed in the acidic solution 13 having a high specific gravity. The generated fine particles 11a are unlikely to settle, and the generated particles 11a are subjected to isotropic pressure from the surroundings because the periphery of the particles 11a is a medium having a high specific gravity. As a result, while the particles 11a generated by thermal melting are cooled and become nanocrystals 3, they exist in a suspended state in the acidic solution 13, so that most of the generated nanocrystals 3 have an isotropic shape. Therefore, even when the maximum diameter is close to 20 nm, the nanocrystal 3 having a high sphericity can be included in a large proportion. In this case, the maximum diameter of the particles 11a can be adjusted by the concentration of nitric acid (NO 3 − ) and hydrofluoric acid (F − ) contained in the acidic solution.

また、このようにして調製される半導体粒子ペーストは、ナノ結晶３に近接して安定度定数の高い金属錯体１４が存在しているために、成膜を行ってナノ結晶３の集積膜を形成したときには、ナノ結晶３の周りからは有機分子１５ａが除かれて、金属錯体１４が優先的に介在するようになり、その結果、加熱後にはナノ結晶３の間には無機配位子４が中間層として存在することになる。こうして中間層を介して隣接するナノ結晶３の間隔を狭いものにすることができる。   In addition, the semiconductor particle paste thus prepared has a metal complex 14 having a high stability constant in the vicinity of the nanocrystal 3, so that the integrated film of the nanocrystal 3 is formed by film formation. In this case, the organic molecules 15a are removed from around the nanocrystals 3 and the metal complexes 14 are preferentially interposed. As a result, the inorganic ligands 4 are interposed between the nanocrystals 3 after heating. It exists as an intermediate layer. Thus, the interval between the adjacent nanocrystals 3 through the intermediate layer can be narrowed.

また、本実施形態の半導体粒子ペーストの製法では、酸性溶液１３中で生成したナノ結晶３は空気に触れることなく、有機分子１５ａを含む有機分子溶液１５中に移動し、有機分子１５ａに覆われる状態になることから、生成したナノ結晶３は含まれる酸素量が極めて少ないものとなり、これにより高い量子効果を示すナノ結晶３を得ることができる。   Moreover, in the manufacturing method of the semiconductor particle paste of this embodiment, the nanocrystal 3 produced | generated in the acidic solution 13 moves in the organic molecule solution 15 containing the organic molecule 15a, without touching air, and is covered with the organic molecule 15a. Since it will be in a state, the produced | generated nanocrystal 3 becomes a thing with very little oxygen amount contained, and can obtain the nanocrystal 3 which shows a high quantum effect by this.

次に、混合溶液から有機分子溶液１５だけ分離回収する。分離回収した有機分子溶液１５は有機分子１５ａが金属錯体１４およびナノ結晶３を含む溶液となっており、こうして本実施形態の半導体粒子ペーストを得ることができる。   Next, only the organic molecule solution 15 is separated and recovered from the mixed solution. The separated and recovered organic molecule solution 15 is a solution in which the organic molecules 15a contain the metal complex 14 and the nanocrystal 3, and thus the semiconductor particle paste of this embodiment can be obtained.

最後に、上記工程によって得られた半導体粒子ペーストを半導体基板１の表面に塗布し、乾燥させることにより、ナノ結晶３が無機配位子１４を介して高密度に充填された集積膜７を得ることができる。   Finally, the semiconductor particle paste obtained by the above process is applied to the surface of the semiconductor substrate 1 and dried to obtain the integrated film 7 in which the nanocrystals 3 are filled with high density via the inorganic ligands 14. be able to.

１・・・・・・・・・・半導体基板
３・・・・・・・・・・ナノ結晶
５・・・・・・・・・・集積膜
１１・・・・・・・・・半導体素原料粒子
１１ａ・・・・・・・・粒子
１３・・・・・・・・・硝酸とフッ酸とを含む酸性溶液
１４・・・・・・・・・無機配位子
１５・・・・・・・・・有機分子溶液
１５ａ・・・・・・・・有機分子 DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate 3 ... Nanocrystal 5 ... Integrated film 11 ... Semiconductor Raw material particles 11a ... Particles 13 ... An acidic solution 14 containing nitric acid and hydrofluoric acid ... Inorganic ligands 15 ...・ ・ ・ ・ ・ ・ Organic molecule solution 15a ... Organic molecules

Claims (6)

金属錯体を含む有機分子の溶液中に、最大径が１〜２０ｎｍで、発光性を示すナノ結晶が分散していることを特徴とする半導体粒子ペースト。   A semiconductor particle paste characterized in that nanocrystals having a maximum diameter of 1 to 20 nm and exhibiting luminescent properties are dispersed in a solution of an organic molecule containing a metal complex. 前記有機分子が、エチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセンから選ばれる少なくとも１種であることを特徴とする請求項１に記載の半導体粒子ペースト。   The organic molecule is selected from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene The semiconductor particle paste according to claim 1, wherein the semiconductor particle paste is at least one kind. 前記金属錯体が、ヘモグロビン、ミオグロビン、クロロフィル、ブレオマイシン、ビタミンＢ１２、モリブトテンヘモシニアン、フェレドキシンの群から選ばれる１種であることを特徴とする請求項１に記載の半導体粒子ペースト。 2. The semiconductor particle paste according to claim 1, wherein the metal complex is one selected from the group consisting of hemoglobin, myoglobin, chlorophyll, bleomycin, vitamin B 12 , molybtoten hemocyanin, and ferredoxin. 前記金属錯体が、Ｎａ、Ｋ、Ｍｇ、Ｃａ、Ａｌ、Ｍｎ、Ｃｏ、Ｆｅ、Ｃｕ、Ｚｎ、Ｍｏ、ＰｄおよびＰｔの群から選ばれる少なくとも１種の金属イオンと、ＣＯ３ ２−、ＮＯ３ −、ＮＨ３、ＲＮＨ２、ＲＣＯＯ−、ＲＯ−、ＲＯＨ、Ｎ２Ｈ４、ＰＯ４ ３−、ＲＯＰＯ３ ２−、（ＲＯ）２ＰＯ２−の群から選ばれる１種の配位子とを含むものであることを特徴とする請求項１に記載の半導体粒子ペースト。 The metal complex includes at least one metal ion selected from the group consisting of Na, K, Mg, Ca, Al, Mn, Co, Fe, Cu, Zn, Mo, Pd, and Pt, CO 3 2− , NO 3. -, NH 3, RNH 2, RCOO -, RO -, ROH, N 2 H 4, PO 4 3-, ROPO 3 2-, and one ligand selected from (RO) 2 PO 2- group The semiconductor particle paste according to claim 1, comprising: 半導体基板の主面上に、請求項１乃至４のうちいずれかの前記半導体粒子ペーストに含まれる前記ナノ結晶の集積膜を有していることを特徴とする光電変換装置。   A photoelectric conversion device comprising an integrated film of the nanocrystals contained in the semiconductor particle paste according to any one of claims 1 to 4 on a main surface of a semiconductor substrate. 前記ナノ結晶が前記金属錯体に由来する無機配位子を介して連結されていることを特徴とする請求項５に記載の光電変換装置。   The photoelectric conversion device according to claim 5, wherein the nanocrystals are linked through an inorganic ligand derived from the metal complex.
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