JPH0567563B2 - - Google Patents
Info
- Publication number
- JPH0567563B2 JPH0567563B2 JP1997789A JP1997789A JPH0567563B2 JP H0567563 B2 JPH0567563 B2 JP H0567563B2 JP 1997789 A JP1997789 A JP 1997789A JP 1997789 A JP1997789 A JP 1997789A JP H0567563 B2 JPH0567563 B2 JP H0567563B2
- Authority
- JP
- Japan
- Prior art keywords
- element selected
- metal chalcogenide
- general formula
- composition
- materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 150000004770 chalcogenides Chemical class 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 229910052714 tellurium Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Description
［技術分野］
本発明は多元系金属カルコゲナイドに関するも
のである。
［従来技術］
金属カルコゲナイドは、酸素に較べてカルコゲ
ナイド（Ｓ、Se、Te）の電気陰性度が小さいた
め、金属オキサイドに較べてイオン性が小さく共
有結合性が大きい。それ故、本質的に結合の異方
性が大きく、低次元性（層状、鎖状、チヤンネル
構造等）の物質を形成し易い。また、物性的には
カルコゲンの電子の最高被占準位が酸素のそれよ
りも浅いために、オキサイドが、主として絶縁体
やバンドギヤツプの大きい半導体を形成するのに
対し、カルコゲナイドは、良電導体やバンドギヤ
ツプの小さい半導体を形成しやすい。金属カルコ
ゲナイドはこれらの構造的、物性的特徴を生かし
て、光学材料（太陽電池、非線型光学材料、発光
材料）、超電導材料（特にシエブレル化合物）、リ
チウム電池材料等への幅広い応用が期待され、既
に一部は実用化されている。
現在実用に供されているセラミツクス材料の大
半はオキサイドであるが、今後素材・材料に対す
る要求がますます多様化していく中にあつて、前
述したようにオキサイドにない特徴を持つ金属カ
ルコゲナイドを、素材・材料として開拓する必要
性は更に高まると予想される。その場合に重要な
ことは、物質群（化合物群）の数を多くそろえる
ことであるが、３元系（金属二種）以上の金属カ
ルコゲナイドは、チオスピネル、カルコパライ
ト、シエブレル等２〜３の物質群を形成すること
が知られているだけである。
［発明が解決しようとする問題点］
本発明は金属を多種含む新規な金属カルコゲナ
イドを提供する。
［問題点を解決するための手段］
本発明者らは、前記を解決すべく種々研究を重
ねた結果、本発明を完成するに至つた。
即ち、本発明によれば、下記一般式（）〜
（）で表される組成を有する新規な多元系金属
カルコゲナイドが提供される。これらのものはほ
とんど同一の結晶構造を有するものである。
一般式（） AxByCz
（但し、式中、ＡはBi、Sb及びAsの中から選ば
れる少なくとも１種の元素、ＢはTi、Ｖ、Nb及
びTaの中から選ばれる少なくとも１種の元素、
ＣはＳ、Se及びTeの中から選ばれる少なくとも
１種の元素を示し、ｘは0.8≦ｘ≦1.2の数、ｙは
1.6≦ｙ≦2.4の数及びｚは4.0≦ｚ≦6.0の数を示
すものである。）
一般式（） AxByCz
（但し、式中、ＡはPb、Sn及びGeの中から選ば
れる少なくとも１種の元素、ＢはTi、Ｖ、Nb及
びTaの中から選ばれる少なくとも１種の元素、
ＣはＳ、Se及びTeの中から選ばれる少なくとも
１種の元素を示し、ｘは0.8≦ｘ≦1.2の数、ｙは
1.6≦ｙ≦2.4の数及びｚは4.0≦ｚ≦6.0の数を示
すものである。）
一般式（） A(1-a)xA′axByCz
（但し、式中、ＡはBi、Sb及びAsの中から選ば
れる少なくとも１種の元素、A′はPb、Sn及びGe
の中から選ばれる少なくとも１種の元素、Ｂは
Ti、Ｖ、Nb及びTaの中から選ばれる少なくとも
１種の元素、ＣはＳ、Se及びTeの中から選ばれ
る少なくとも１種の元素を示し、ａは０≦ａ≦１
の数、ｘは0.8≦ｘ≦1.2の数、ｙは1.6≦ｙ≦2.4
の数及びｚは4.0≦ｚ≦6.0の数を示すものであ
る。）
本発明の多元系金属カルコゲナイドは、前記組
成に対応する成分の元素粉末あるいは金属カルコ
ゲナイド粉末を、その組成割合に秤取して、石英
等の耐熱耐酸化性容器中に真空封入し、400〜
1200℃で加熱処理した後、室温まで冷却すること
によつて製造することができる。
このようにして得られたものは、褐色から黒色
の粉末で、粉末Ｘ線回折パターンがほとんど１つ
の面からの回折線をみを示す。また条件によつて
は薄片状結晶が得られ、それが容易に劈開するこ
ととあわせ、何らかの層状構造を持つと推定され
る。
［発明の効果］
本発明の多元系金属カルコゲナイドは、太陽電
池、非線型光学材料、発光材料等の光学材料や、
超電導材料、リチウム電池材料等として利用され
る。
［実施例］
次に本発明を実施例により、さらに詳細に説明
する。
実施例 １
前記一般式（）の組成に対応する金属カルコ
ゲナイドを次のようにして合成した。
第１表の組成に対応する元素粉末をその組成割
合に採取し、石英容器中に真空封入した後、400
〜1200℃の温度に加熱し、次いで室温まで冷却し
た。このようにして得られた金属カルコゲナイド
の具体的組成と、その粉末Ｘ線回折パターンにお
ける主な回折線の面間隔（Å）を第１表に示す。
なお、本発明の金属カルコゲナイドにおいて
は、その成分ＡとＢとＣの組成は、通常、１：
２：５と表示されるが、Ｃ成分にはノンストイキ
オメトリーがあるので正確な５の値ではなく、
4.0〜6.0の範囲にある。また、成分Ａ及びＢも同
様に、その値は正確な１ではなくＡは0.8〜1.2の
範囲に、Ｂは1.6〜2.4の範囲にあるものと考えら
れる。
実施例 ２
前記一般式（）の組成に対応する金属カルコ
ゲナイドを実施例１と同様にして合成し、その具
体的組成と、粉末Ｘ線回折パターンにおける主な
回折線の面間隔（Å）を第２表に示す。
実施例 ３
前記一般式（）の組成に対応する金属カルコ
ゲナイドを実施例１と同様にして合成し、その具
体的組成と、粉末Ｘ線回折パターンにおける主な
回折線の面間隔（Å）を第３表に示す。
[Technical Field] The present invention relates to multi-element metal chalcogenides. [Prior Art] Metal chalcogenides (S, Se, Te) have lower electronegativity than oxygen, and therefore have less ionicity and greater covalent bonding than metal oxides. Therefore, the anisotropy of bonding is essentially large, and it is easy to form a substance with low dimensionality (layered, chained, channel structure, etc.). In addition, in physical terms, the highest occupied level of chalcogen electrons is shallower than that of oxygen, so oxides mainly form insulators and semiconductors with large band gaps, whereas chalcogenides are good conductors and It is easy to form semiconductors with small band gaps. Taking advantage of these structural and physical characteristics, metal chalcogenides are expected to have a wide range of applications such as optical materials (solar cells, nonlinear optical materials, light-emitting materials), superconducting materials (particularly Siebrel compounds), and lithium battery materials. Some of them have already been put into practical use. The majority of ceramic materials currently in practical use are oxides, but as requirements for materials become more and more diverse in the future, metal chalcogenides, which have characteristics not found in oxides, are being developed as materials.・The need to develop it as a material is expected to further increase. In that case, the important thing is to have a large number of substance groups (compound groups), but metal chalcogenides of ternary system (two metals) or more are made of two or three substance groups such as thiospinel, chalcopalite, and siebrel. It is only known to form. [Problems to be Solved by the Invention] The present invention provides a novel metal chalcogenide containing various metals. [Means for Solving the Problems] The present inventors have conducted various studies to solve the above problems, and as a result, have completed the present invention. That is, according to the present invention, the following general formula () ~
A novel multi-component metal chalcogenide having a composition represented by () is provided. These substances have almost the same crystal structure. General formula () AxByCz (wherein, A is at least one element selected from Bi, Sb and As, B is at least one element selected from Ti, V, Nb and Ta,
C represents at least one element selected from S, Se, and Te, x is a number of 0.8≦x≦1.2, and y is
The number 1.6≦y≦2.4 and z indicate the number 4.0≦z≦6.0. ) General formula () AxByCz (However, in the formula, A is at least one element selected from Pb, Sn and Ge, B is at least one element selected from Ti, V, Nb and Ta,
C represents at least one element selected from S, Se, and Te, x is a number of 0.8≦x≦1.2, and y is
The number 1.6≦y≦2.4 and z indicate the number 4.0≦z≦6.0. ) General formula () A (1-a)x A′axByCz (However, in the formula, A is at least one element selected from Bi, Sb, and As, and A′ is Pb, Sn, and Ge.
At least one element selected from B is
At least one element selected from Ti, V, Nb and Ta; C represents at least one element selected from S, Se and Te; a is 0≦a≦1
The number of , x is the number of 0.8≦x≦1.2, y is the number of 1.6≦y≦2.4
The number and z indicate a number of 4.0≦z≦6.0. ) The multi-component metal chalcogenide of the present invention is produced by weighing elemental powders or metal chalcogenide powders having components corresponding to the above-mentioned composition in their composition ratios, vacuum-sealing them in a heat-resistant, oxidation-resistant container such as quartz, etc.
It can be produced by heating at 1200°C and then cooling to room temperature. The product thus obtained is a brown to black powder with a powder X-ray diffraction pattern showing mostly only diffraction lines from one plane. In addition, depending on the conditions, flaky crystals can be obtained, and since they are easily cleaved, it is assumed that they have some kind of layered structure. [Effects of the Invention] The multi-component metal chalcogenide of the present invention can be used in optical materials such as solar cells, nonlinear optical materials, and luminescent materials;
Used as superconducting material, lithium battery material, etc. [Example] Next, the present invention will be explained in more detail with reference to Examples. Example 1 A metal chalcogenide corresponding to the composition of the above general formula () was synthesized as follows. Elemental powders corresponding to the compositions in Table 1 were collected in the proportions, vacuum-sealed in a quartz container, and then
Heated to a temperature of ~1200°C and then cooled to room temperature. Table 1 shows the specific composition of the metal chalcogenide thus obtained and the interplanar spacing (Å) of the main diffraction lines in its powder X-ray diffraction pattern. In addition, in the metal chalcogenide of the present invention, the composition of components A, B, and C is usually 1:
It is displayed as 2:5, but since the C component has non-stoichiometry, it is not the exact value of 5,
It ranges from 4.0 to 6.0. Similarly, the values of components A and B are not exactly 1, but A is considered to be in the range of 0.8 to 1.2, and B is considered to be in the range of 1.6 to 2.4. Example 2 A metal chalcogenide corresponding to the composition of the general formula () was synthesized in the same manner as in Example 1, and its specific composition and interplanar spacing (Å) of the main diffraction lines in the powder X-ray diffraction pattern were determined. It is shown in Table 2. Example 3 A metal chalcogenide corresponding to the composition of the general formula () was synthesized in the same manner as in Example 1, and its specific composition and interplanar spacing (Å) of the main diffraction lines in the powder X-ray diffraction pattern were determined. It is shown in Table 3.
【表】【table】
【表】【table】
Claims (1)
れる少なくとも１種の元素、ＢはTi、Ｖ、Nb及
びTaの中から選ばれる少なくとも１種の元素、
ＣはＳ、Se及びTeの中から選ばれる少なくとも
１種の元素を示し、ｘは0.8≦ｘ≦1.2の数、ｙは
1.6≦ｙ≦2.4の数及びｚは4.0≦ｚ≦6.0の数を示
すものである。）で表される組成を有することを
特徴とする多元系金属カルコゲナイド。 ２ 一般式 AxByCz （） （但し、式中、ＡはPb、Sn及びGeの中から選ば
れる少なくとも１種の元素、ＢはTi、Ｖ、Nb及
びTaの中から選ばれる少なくとも１種の元素、
ＣはＳ、Se及びTeの中から選ばれる少なくとも
１種の元素を示し、ｘは0.8≦ｘ≦1.2の数、ｙは
1.6≦ｙ≦2.4の数及びｚは4.0≦ｚ≦6.0の数を示
すものである。）で表される組成を有することを
特徴とする多元系金属カルコゲナイド。 ３ 一般式 A(1-a)xA′axByCz （） （但し、式中、ＡはBi、Sb及びAsの中から選ば
れる少なくとも１種の元素、A′はPb、Sn及びGe
の中から選ばれる少なくとも１種の元素、Ｂは
Ti、Ｖ、Nb及びTaの中から選ばれる少なくとも
１種の元素、ＣはＳ、Se及びTeの中から選ばれ
る少なくとも１種の元素を示し、ａは０≦ａ≦１
の数、ｘは0.8≦ｘ≦1.2の数、ｙは1.6≦ｙ≦2.4
の数及びｚは4.0≦ｚ≦6.0の数を示すものであ
る。）で表される組成を有することを特徴とする
多元系金属カルコゲナイド。[Claims] 1 General formula AxByCz () (wherein A is at least one element selected from Bi, Sb, and As, and B is selected from Ti, V, Nb, and Ta) at least one element,
C represents at least one element selected from S, Se, and Te, x is a number of 0.8≦x≦1.2, and y is
The number 1.6≦y≦2.4 and z indicate the number 4.0≦z≦6.0. ) A multi-element metal chalcogenide characterized by having a composition represented by: 2 General formula AxByCz () (wherein A is at least one element selected from Pb, Sn and Ge, B is at least one element selected from Ti, V, Nb and Ta,
C represents at least one element selected from S, Se, and Te, x is a number of 0.8≦x≦1.2, and y is
The number 1.6≦y≦2.4 and z indicate the number 4.0≦z≦6.0. ) A multi-element metal chalcogenide characterized by having a composition represented by: 3 General formula A (1-a)x A′axByCz () (However, in the formula, A is at least one element selected from Bi, Sb, and As, and A′ is Pb, Sn, and Ge.
At least one element selected from B is
At least one element selected from Ti, V, Nb and Ta; C represents at least one element selected from S, Se and Te; a is 0≦a≦1
The number of , x is the number of 0.8≦x≦1.2, y is the number of 1.6≦y≦2.4
The number and z indicate a number of 4.0≦z≦6.0. ) A multi-element metal chalcogenide characterized by having a composition represented by:
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1997789A JPH02199006A (en) | 1989-01-30 | 1989-01-30 | Multielement-based metal chalocogenide having 1/2/5 composition |
| US07/446,548 US5051204A (en) | 1988-11-30 | 1989-11-28 | Multi-element metal chalocogenide |
| DE89312411T DE68908108T2 (en) | 1988-11-30 | 1989-11-29 | Multi-element metal chalcogenide. |
| EP89312411A EP0371780B1 (en) | 1988-11-30 | 1989-11-29 | Multi-element metal chalcogenide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1997789A JPH02199006A (en) | 1989-01-30 | 1989-01-30 | Multielement-based metal chalocogenide having 1/2/5 composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02199006A JPH02199006A (en) | 1990-08-07 |
| JPH0567563B2 true JPH0567563B2 (en) | 1993-09-27 |
Family
ID=12014247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1997789A Granted JPH02199006A (en) | 1988-11-30 | 1989-01-30 | Multielement-based metal chalocogenide having 1/2/5 composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02199006A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0611642B2 (en) * | 1989-03-14 | 1994-02-16 | 工業技術院長 | Layered metal chalcogenide host material |
| KR101463195B1 (en) * | 2011-04-28 | 2014-11-21 | 주식회사 엘지화학 | New compound semiconductors and their application |
| JP5774141B2 (en) * | 2011-04-28 | 2015-09-02 | エルジー・ケム・リミテッド | New compound semiconductors and their utilization |
| JP5767395B2 (en) * | 2011-05-13 | 2015-08-19 | エルジー・ケム・リミテッド | New compound semiconductors and their utilization |
| EP2708503B1 (en) * | 2011-05-13 | 2017-02-15 | LG Chem, Ltd. | Novel compound semiconductor and usage for same |
| CN103517870B (en) * | 2011-05-13 | 2016-02-03 | Lg化学株式会社 | New compound semiconductor and uses thereof |
-
1989
- 1989-01-30 JP JP1997789A patent/JPH02199006A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02199006A (en) | 1990-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Foecker et al. | The atomic order of the pnictogen and chalcogen atoms in equiatomic ternary compounds TPnCh (T= Ni, Pd; Pn= P, As, Sb; Ch= S, Se, Te) | |
| Mansuetto et al. | Synthesis and structures of the new group IV chalcogenides NaCuTiS3 and NaCuZrQ3 (Q= S, Se, Te) | |
| Zeilinger et al. | Structural and thermodynamic similarities of phases in the Li–Tt (Tt= Si, Ge) systems: redetermination of the lithium-rich side of the Li–Ge phase diagram and crystal structures of Li 17 Si 4.0− x Ge x for x= 2.3, 3.1, 3.5, and 4 as well as Li 4.1 Ge | |
| Sleight et al. | Chromium chalcogenides prepared at high pressure and the crystal growth of chromium sesquisulfide | |
| JPH0567563B2 (en) | ||
| Huan et al. | Antiferromagnetic-to-ferromagnetic transition in metallic Tl1− xKxCo2Se2 (0⩽ x⩽ 1.0) with ThCr2Si2-type structure | |
| US5051204A (en) | Multi-element metal chalocogenide | |
| US5708233A (en) | Thermoelectric semiconductor material | |
| US3940472A (en) | Quaternary sulfides and selenides containing Ba or Sr and selected transition metals | |
| US3851045A (en) | Lanthanide transition metal ternary chalcogenides | |
| US3211656A (en) | Mixed-crystal thermoelectric composition | |
| Xia et al. | Synthesis, crystal structures, magnetic and electric transport properties of Eu11InSb9 and Yb11InSb9 | |
| US4545967A (en) | Stabilized lanthanum sulphur compounds | |
| JPH0547482B2 (en) | ||
| Noel | New sulfides of uranium and 3d transition series elements | |
| Tenorio et al. | Filamentary superconductivity in semiconducting policrystalline ZrSe 2 compound with Zr vacancies | |
| Patschke et al. | Rb 2 Cu 3 CeTe 5: a quaternary semiconducting compound with a two-dimensional polytelluride framework | |
| Schwarz et al. | The new barium zinc mercurides Ba3ZnHg10 and BaZn0. 6Hg3. 4–Synthesis, crystal and electronic structure | |
| Küpers et al. | Preferred selenium incorporation and unexpected interlayer bonding in the layered structure of Sb2Te3− x Se x | |
| Isaeva et al. | New metal-rich mixed chalcogenides with intergrowth structures: Ni8. 21Ge2S2 and Ni8. 45Ge2Se2 | |
| US3676082A (en) | Magnetic compositions | |
| Korzun et al. | Preparation of Alloys and Investigation of Phase Equilibria in the CuFeS 2− δ–CuGaS 2 System | |
| Menezes et al. | La 12 Sb 9 S 38: a new semiconducting lanthanum antimony polysulfide with a mixed La/Sb site | |
| Bobev et al. | Synthesis, characterization and bonding of Ba3Li4Sn8 | |
| Zhou et al. | Synthesis, crystal structure and physical properties of a novel quaternary selenide Cu6GeWSe8 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |