CN106904652B - A kind of pentatomic sulphur antimonial semi-conducting material and its production and use - Google Patents
A kind of pentatomic sulphur antimonial semi-conducting material and its production and use Download PDFInfo
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Abstract
本发明公开了一种五元硫锑化合物半导体材料及其制备方法和用途。以碱金属盐、碱土金属氢氧化物、金属铜、二元固溶体Sb2S3和单质S为原料，聚乙二醇，丙二胺，水合肼为溶剂，在140℃烘箱中反应5‑7天，得到五元硫属化合物半导体材料。化学组成式分别为：K2Ba3Cu2Sb2S10,Rb2Ba3Cu2Sb2S10和Cs2Ba3Cu2Sb2S10，本发明的化合物具有新的骨架结构，制备原料简单且成本低，反应条件温和，合成温度低。采用本发明得到的五元硫属化合物可用于制备光学半导体器件或太阳能电池过渡层材料。The invention discloses a five-membered sulfur-antimony compound semiconductor material, a preparation method and application thereof. Using alkali metal salts, alkaline earth metal hydroxides, metal copper, binary solid solution Sb 2 S 3 and simple S as raw materials, polyethylene glycol, propylenediamine, and hydrazine hydrate as solvents, react in an oven at 140°C for 5‑7 One day, a five-membered chalcogenide semiconductor material was obtained. The chemical composition formulas are: K 2 Ba 3 Cu 2 Sb 2 S 10 , Rb 2 Ba 3 Cu 2 Sb 2 S 10 and Cs 2 Ba 3 Cu 2 Sb 2 S 10 , the compound of the present invention has a new skeleton structure, and the preparation The raw materials are simple and low in cost, the reaction conditions are mild, and the synthesis temperature is low. The five-membered chalcogen compound obtained by the invention can be used to prepare optical semiconductor devices or transition layer materials of solar cells.
Description
技术领域technical field
本发明属于无机半导体材料领域，具体涉及一种五元硫锑化合物半导体材料及其制备方法和用途。The invention belongs to the field of inorganic semiconductor materials, and in particular relates to a five-element sulfur-antimony compound semiconductor material and its preparation method and application.
背景技术Background technique
在过去的几十年间，硫属化合物的研究从未间断，由于其结构的丰富性导致的物理化学性能多样性，在非线性光学，离子交换，光催化，太阳能电池等领域有极大的潜在应用价值。第五主族元素由于孤对电子的存在，因而可以拥有灵活的配位结构，因此常被用于制备各种新结构的化合物。对于拥有5s2电子对的Sb3+离子来说，锑与硫属元素组成的结构单元[SbIIIQx]3-(x＝3,4,5)也由此可以在不同结构导向剂的调控下，与有机或无机的正电荷单元组成大量结构各异的硫属化合物。In the past few decades, the research on chalcogenides has never stopped. Due to the diversity of physical and chemical properties caused by its rich structure, it has great potential in the fields of nonlinear optics, ion exchange, photocatalysis, and solar cells. Value. Due to the existence of lone pairs of electrons, the elements of the fifth main group can have flexible coordination structures, so they are often used to prepare compounds with various new structures. For Sb 3+ ions with 5s 2 electron pairs, the structural unit [Sb III Qx] 3- (x=3,4,5) composed of antimony and chalcogen can also be controlled by different structure directing agents. Under these conditions, a large number of chalcogenides with different structures can be formed with organic or inorganic positively charged units.
硫属化合物中碱金属和碱土金属离子由于其半径和电荷的差异，会对MxQy(M＝过渡金属Q＝硫属元素)结构单元的连接产生不同影响，从而改变多元化合物的结构。已经合成的包含过渡金属的无机四元硫属化合物诸如Cs2Cu2Sb2Se5，K2CuSbS3，Rb2Cu2Sb2S5以及KCu2SbS3都属于碱金属正离子位于二维骨架之间的层状结构化合物，但是最近合成的硫锑化合物结构中，同样包含碱金属正离子的ACuSb2S4(A＝Rb,Cs)呈现的是三维骨架结构。包含碱土金属的化合物过去合成较少，新合成的BaCuSbQ3(Q＝S,Se)也属于三维孔道结构。对于同时包含碱金属以及碱土金属正离子的硫属化合物晶体，在目前的报道中大多数呈现出零维结构，例如KBaNbS4，K4Ba2(Nb2S11)2，K4Ba[VS4]2，KBa4(BS3)3，K4Ba11(BS3)8S以及ABaMQ4(A＝Rb,Cs；M＝V,P；Q＝S,Se)。KBaMSe3(M＝As,Sb)作为其中唯一的硫属锑化物，K+，Ba2+离子位于独立的MSe3(M＝As,Sb)三角锥之间，同样具有零维结构。由此可见，化合物中正离子的存在方式，影响着硫属化合物的整体骨架结构。Due to the difference in radius and charge, alkali metal and alkaline earth metal ions in chalcogenides will have different effects on the connection of M x Q y (M = transition metal Q = chalcogen) structural units, thereby changing the structure of the multi-component compound. The synthesized inorganic quaternary chalcogenides containing transition metals such as Cs 2 Cu 2 Sb 2 Se 5 , K 2 CuSbS 3 , Rb 2 Cu 2 Sb 2 S 5 and KCu 2 SbS 3 are all alkali metal cations located in the two-dimensional A compound with a layered structure between the skeletons, but in the recently synthesized sulfur-antimony compound structure, ACuSb 2 S 4 (A=Rb, Cs), which also contains alkali metal cations, presents a three-dimensional skeleton structure. Compounds containing alkaline earth metals were seldom synthesized in the past, and the newly synthesized BaCuSbQ 3 (Q=S, Se) also belongs to the three-dimensional pore structure. For chalcogenide crystals containing both alkali metal and alkaline earth metal cations, most of the current reports present a zero-dimensional structure, such as KBaNbS 4 , K 4 Ba 2 (Nb 2 S 11 ) 2 , K 4 Ba[VS 4 ] 2 , KBa 4 (BS 3 ) 3 , K 4 Ba 11 (BS 3 ) 8 S and ABaMQ 4 (A=Rb,Cs; M=V,P; Q=S,Se). KBaMSe 3 (M=As, Sb) is the only chalcogen antimonide, and K + , Ba 2+ ions are located between independent MSe 3 (M=As, Sb) triangular pyramids, which also have a zero-dimensional structure. It can be seen that the existence of positive ions in the compound affects the overall skeleton structure of the chalcogen compound.
溶剂热法是有效的合成多元硫属化合物的手段。通过在溶剂热反应中使用不同有机胺作为还原剂，不同表面活性剂作为结构导向剂，我们同样能够得到不同维度的骨架结构。开发新的溶剂热合成路线,寻找新的合成体系,合成具有优良物理化学性能的结构是目前合成新型多元硫属化物的重点，也是相关研究关注的问题。Solvothermal method is an effective method for the synthesis of polychalcogenides. By using different organic amines as reducing agents and different surfactants as structure-directing agents in the solvothermal reaction, we can also obtain skeleton structures of different dimensions. Developing new solvothermal synthesis routes, finding new synthetic systems, and synthesizing structures with excellent physical and chemical properties are currently the focus of synthesizing new multi-component chalcogenides, and they are also issues of concern in related research.
发明内容Contents of the invention
本发明的目的在于解决现有技术中存在的问题，并提供一种五元硫锑化合物半导体材料及其制备方法。本发明采用的具体技术方案如下：The purpose of the present invention is to solve the problems existing in the prior art, and provide a pentavalent sulfur-antimony compound semiconductor material and a preparation method thereof. The concrete technical scheme that the present invention adopts is as follows:
五元硫锑化合物半导体材料，其化学组成式为以下三种之一，分别为：K2Ba3Cu2Sb2S10,Rb2Ba3Cu2Sb2S10和Cs2Ba3Cu2Sb2S10，三种化合物为同构；Pentasulfide antimony compound semiconductor material, its chemical composition formula is one of the following three types: K 2 Ba 3 Cu 2 Sb 2 S 10 , Rb 2 Ba 3 Cu 2 Sb 2 S 10 and Cs 2 Ba 3 Cu 2 Sb 2 S 10 , the three compounds are isomorphic;
其中K2Ba3Cu2Sb2S10属于单斜晶系，C2/m空间群，晶胞参数 α＝90°，β＝115.257(13)°，γ＝90°， Z＝2，Dc＝4.605g/cm3，单晶体为深红色块状。Among them, K 2 Ba 3 Cu 2 Sb 2 S 10 belongs to monoclinic crystal system, C2/m space group, unit cell parameters α=90°, β=115.257(13)°, γ=90°, Z = 2, D c = 4.605g/cm 3 , the single crystal is dark red block.
其中Rb2Ba3Cu2Sb2S10属于单斜晶系，C2/m空间群，晶胞参数 α＝90°，β＝115.992(11)°，γ＝90°， Z＝2，Dc＝4.332g/cm3，单晶体为深红色块状，能隙为1.7eV，模拟太阳光照射下光电流约为4μA/cm2。Among them, Rb 2 Ba 3 Cu 2 Sb 2 S 10 belongs to monoclinic crystal system, C2/m space group, unit cell parameters α=90°, β=115.992(11)°, γ=90°, Z = 2, D c = 4.332g/cm 3 , the single crystal is dark red bulk, the energy gap is 1.7eV, and the photocurrent is about 4μA/cm 2 under simulated sunlight irradiation.
其中Cs2Ba3Cu2Sb2S10属于单斜晶系，C2/m空间群，晶胞参数 α＝90°，β＝116.514(15)°，γ＝90°， Z＝2，Dc＝4.524g/cm3，单晶体为深红色块状。Among them, Cs 2 Ba 3 Cu 2 Sb 2 S 10 belongs to monoclinic system, C2/m space group, unit cell parameters α=90°, β=116.514(15)°, γ=90°, Z = 2, D c = 4.524g/cm 3 , the single crystal is dark red block.
五元硫锑化合物半导体材料K2Ba3Cu2Sb2S10的制备方法，具体为：将摩尔比为1.0-1.5：1.3-0.8：0.5-1.0：0.25：2.0-2.5的氢氧化钡、氢氧化钾、金属铜、二元固溶体硫化锑和单质硫混合，以2.0mL聚乙二醇(PEG400)，0.5mL 85wt％水合肼，0.5mL丙二胺为溶剂，在140℃下中反应5-7天，经去离子水和乙醇洗涤后得到K2Ba3Cu2Sb2S10。The preparation method of the pentavalent sulfur-antimony compound semiconductor material K 2 Ba 3 Cu 2 Sb 2 S 10 is specifically as follows: barium hydroxide, Potassium hydroxide, metal copper, binary solid solution antimony sulfide and elemental sulfur were mixed, with 2.0mL polyethylene glycol (PEG400), 0.5mL 85wt% hydrazine hydrate, 0.5mL propylenediamine as solvent, and reacted at 140°C for 5 -7 days, K 2 Ba 3 Cu 2 Sb 2 S 10 was obtained after washing with deionized water and ethanol.
五元硫锑化合物半导体材料Rb2Ba3Cu2Sb2S10的制备方法，具体为：将摩尔比为1.0：1.3-0.8：0.5-1.0：0.25：2.0-2.5的氢氧化钡、氯化铷、金属铜、二元固溶体硫化锑和单质硫混合，以2.0mL聚乙二醇(PEG400)，0.5-1.0mL 85wt％水合肼，0-0.5mL丙二胺为溶剂，在140℃下中反应5-7天，经去离子水和乙醇洗涤后得到Rb2Ba3Cu2Sb2S10。The preparation method of the five-element sulfur-antimony compound semiconductor material Rb 2 Ba 3 Cu 2 Sb 2 S 10 is specifically as follows: barium hydroxide, chloride Rubidium, metal copper, binary solid solution antimony sulfide and elemental sulfur are mixed, with 2.0mL polyethylene glycol (PEG400), 0.5-1.0mL 85wt% hydrazine hydrate, 0-0.5mL propylenediamine as solvent, and neutralized at 140°C After reacting for 5-7 days, Rb 2 Ba 3 Cu 2 Sb 2 S 10 was obtained after washing with deionized water and ethanol.
五元硫锑化合物半导体材料Cs2Ba3Cu2Sb2S10的制备方法，具体为：将摩尔比为1.0-1.5：1.3-0.8：0.5-1.0：0.25：2.0-2.5的氢氧化钡、氢氧化铯、金属铜、二元固溶体硫化锑和单质硫混合，以2.0mL聚乙二醇400，0.5mL 85wt％水合肼，0.5mL丙二胺为溶剂，在140℃下中反应5-7天，经去离子水和乙醇洗涤后得到Cs2Ba3Cu2Sb2S10。The preparation method of the pentavalent sulfur antimony compound semiconductor material Cs 2 Ba 3 Cu 2 Sb 2 S 10 specifically comprises: barium hydroxide, Cesium hydroxide, metal copper, binary solid solution antimony sulfide and elemental sulfur are mixed, and 2.0mL polyethylene glycol 400, 0.5mL 85wt% hydrazine hydrate, 0.5mL propylenediamine are used as solvents, and the reaction is carried out at 140°C for 5-7 Cs 2 Ba 3 Cu 2 Sb 2 S 10 was obtained after washing with deionized water and ethanol.
上述五元硫锑化合物半导体材料可用于制备光电化学半导体器件或太阳能电池过渡层材料。The above-mentioned pentavalent sulfur-antimony compound semiconductor material can be used to prepare photoelectrochemical semiconductor devices or solar cell transition layer materials.
本发明的有益效果：合成具有新结构的化合物，原料成本低，反应条件温和。采用本方法制备的五元硫锑化合物半导体材料，产率可达到～50％。半导体材料Rb2Ba3Cu2Sb2S10的能隙为1.7eV，在模拟太阳光下的光电流为4μA/cm2，在半导体光学及太阳能电池方面具有潜在的应用价值。The beneficial effect of the present invention is that the compound with a new structure is synthesized, the raw material cost is low, and the reaction conditions are mild. The yield of the five-element sulfur-antimony compound semiconductor material prepared by the method can reach ~50%. The semiconductor material Rb 2 Ba 3 Cu 2 Sb 2 S 10 has an energy gap of 1.7eV and a photocurrent of 4μA/cm 2 under simulated sunlight, which has potential application value in semiconductor optics and solar cells.
附图说明Description of drawings
图1为a)K2Ba3Cu2Sb2S10,b)Rb2Ba3Cu2Sb2S10和c)Cs2Ba3Cu2Sb2S10晶体的EDX图谱；Figure 1 shows the EDX spectra of a) K 2 Ba 3 Cu 2 Sb 2 S 10 , b) Rb 2 Ba 3 Cu 2 Sb 2 S 10 and c) Cs 2 Ba 3 Cu 2 Sb 2 S 10 crystals;
图2为Rb2Ba3Cu2Sb2S10晶体的结构图；Figure 2 is a structural diagram of Rb 2 Ba 3 Cu 2 Sb 2 S 10 crystal;
图3为根据Rb2Ba3Cu2Sb2S10晶体得到的的XRD图谱与单晶模拟衍射对比图；Figure 3 is a comparison between the XRD pattern obtained from the Rb 2 Ba 3 Cu 2 Sb 2 S 10 crystal and the simulated diffraction pattern of a single crystal;
图4为Rb2Ba3Cu2Sb2S10的固态紫外可见漫反射光谱；Figure 4 is the solid-state UV-Vis diffuse reflectance spectrum of Rb 2 Ba 3 Cu 2 Sb 2 S 10 ;
图5为Rb2Ba3Cu2Sb2S10在模拟太阳光下的光响应图谱。Fig. 5 is a photoresponse spectrum of Rb 2 Ba 3 Cu 2 Sb 2 S 10 under simulated sunlight.
具体实施方式Detailed ways
下面结合附图和实施例对本发明做进一步阐述和说明。本发明中各个实施方式的技术特征在没有相互冲突的前提下，均可进行相应组合。The present invention will be further elaborated and illustrated below in conjunction with the accompanying drawings and embodiments. The technical features of the various implementations in the present invention can be combined accordingly on the premise that there is no conflict with each other.
五元硫锑化合物半导体材料，其化学组成式分别为：K2Ba3Cu2Sb2S10,Rb2Ba3Cu2Sb2S10和Cs2Ba3Cu2Sb2S10，三种化合物为同构。Pentasulfide antimony compound semiconductor material, its chemical composition formula is: K 2 Ba 3 Cu 2 Sb 2 S 10 , Rb 2 Ba 3 Cu 2 Sb 2 S 10 and Cs 2 Ba 3 Cu 2 Sb 2 S 10 , three kinds Compounds are isomorphic.
其中K2Ba3Cu2Sb2S10属于单斜晶系，C2/m空间群，晶胞参数 α＝90°，β＝115.257(13)°，γ＝90°， Z＝2，Dc＝4.605g/cm3，单晶体为深红色块状。Among them, K 2 Ba 3 Cu 2 Sb 2 S 10 belongs to monoclinic crystal system, C2/m space group, unit cell parameters α=90°, β=115.257(13)°, γ=90°, Z = 2, D c = 4.605g/cm 3 , the single crystal is dark red block.
其中Rb2Ba3Cu2Sb2S10属于单斜晶系，C2/m空间群，晶胞参数 α＝90°，β＝115.992(11)°，γ＝90°， Z＝2，Dc＝4.332g/cm3，单晶体为深红色块状，能隙为1.7eV，模拟太阳光照射下光电流为4μA/cm2。Among them, Rb 2 Ba 3 Cu 2 Sb 2 S 10 belongs to monoclinic crystal system, C2/m space group, unit cell parameters α=90°, β=115.992(11)°, γ=90°, Z = 2, D c = 4.332g/cm 3 , the single crystal is dark red bulk, the energy gap is 1.7eV, and the photocurrent under simulated sunlight is 4μA/cm 2 .
其中Cs2Ba3Cu2Sb2S10属于单斜晶系，C2/m空间群，晶胞参数 α＝90°，β＝116.514(15)°，γ＝90°， Z＝2，Dc＝4.524g/cm3，单晶体为深红色块状。Among them, Cs 2 Ba 3 Cu 2 Sb 2 S 10 belongs to monoclinic system, C2/m space group, unit cell parameters α=90°, β=116.514(15)°, γ=90°, Z = 2, D c = 4.524g/cm 3 , the single crystal is dark red block.
五元硫锑化合物半导体材料K2Ba3Cu2Sb2S10的制备方法，具体为：将摩尔比为1.0-1.5：1.3-0.8：0.5-1.0：0.25：2.0-2.5的氢氧化钡、氢氧化钾、金属铜、二元固溶体硫化锑和单质硫混合，以2.0mL聚乙二醇(PEG400)，0.5mL 85wt％水合肼，0.5mL丙二胺为溶剂，在140℃下中反应5-7天，经去离子水和乙醇洗涤后得到K2Ba3Cu2Sb2S10。The preparation method of the pentavalent sulfur-antimony compound semiconductor material K 2 Ba 3 Cu 2 Sb 2 S 10 is specifically as follows: barium hydroxide, Potassium hydroxide, metal copper, binary solid solution antimony sulfide and elemental sulfur were mixed, with 2.0mL polyethylene glycol (PEG400), 0.5mL 85wt% hydrazine hydrate, 0.5mL propylenediamine as solvent, and reacted at 140°C for 5 -7 days, K 2 Ba 3 Cu 2 Sb 2 S 10 was obtained after washing with deionized water and ethanol.
将上述制备方法中的氢氧化钾替换为氢氧化铯，在140℃下中反应5-7天，经去离子水和乙醇洗涤后得到Cs2Ba3Cu2Sb2S10。Potassium hydroxide in the above preparation method is replaced by cesium hydroxide, reacted at 140° C. for 5-7 days, and washed with deionized water and ethanol to obtain Cs 2 Ba 3 Cu 2 Sb 2 S 10 .
五元硫锑化合物半导体材料Rb2Ba3Cu2Sb2S10的制备方法，具体为：将摩尔比为1.0：1.3-0.8：0.5-1.0：0.25：2.0-2.5的氢氧化钡、氯化铷、金属铜、二元固溶体硫化锑和单质硫混合，以2.0mL聚乙二醇(PEG400)，0.5-1.0mL 85wt％水合肼，0-0.5mL丙二胺为溶剂，在140℃下中反应5-7天，经去离子水和乙醇洗涤后得到Rb2Ba3Cu2Sb2S10。The preparation method of the five-element sulfur-antimony compound semiconductor material Rb 2 Ba 3 Cu 2 Sb 2 S 10 is specifically as follows: barium hydroxide, chloride Rubidium, metal copper, binary solid solution antimony sulfide and elemental sulfur are mixed, with 2.0mL polyethylene glycol (PEG400), 0.5-1.0mL 85wt% hydrazine hydrate, 0-0.5mL propylenediamine as solvent, and neutralized at 140°C After reacting for 5-7 days, Rb 2 Ba 3 Cu 2 Sb 2 S 10 was obtained after washing with deionized water and ethanol.
实施例1：Example 1:
K2Ba3Cu2Sb2S10晶体，称取初始原料KOH 0.80mmol(0.048g)、Ba(OH)2·8H2O1.00mmol(0.316g)、Cu 0.50mmol(0.032g)、Sb2S3 0.25mmol(0.085g)和S 2.00mmol(0.064g)放入水热釜中，再加入2.0mL聚乙二醇(PEG400)，0.5mL 85wt％水合肼，0.5mL丙二胺，将水热釜置于140℃下反应7天。产物分别用蒸馏水和无水乙醇洗涤2次，得到产率为10％的深红色厚片状晶体。EDX元素分析表明晶体只含K、Ba、Cu、Sb、S五种元素，且各元素含量比约为2:3:2:2:10。K 2 Ba 3 Cu 2 Sb 2 S 10 crystals, weigh the initial raw materials KOH 0.80mmol (0.048g), Ba(OH) 2 8H 2 O 1.00mmol (0.316g), Cu 0.50mmol (0.032g), Sb 2 Put S 3 0.25mmol (0.085g) and S 2.00mmol (0.064g) into a hydrothermal kettle, then add 2.0mL polyethylene glycol (PEG400), 0.5mL 85wt% hydrazine hydrate, 0.5mL propylenediamine, and water The hot pot was placed at 140°C for 7 days. The product was washed twice with distilled water and absolute ethanol, respectively, to obtain dark red thick flaky crystals with a yield of 10%. EDX elemental analysis shows that the crystal only contains K, Ba, Cu, Sb, and S, and the content ratio of each element is about 2:3:2:2:10.
实施例2：Example 2:
K2Ba3Cu2Sb2S10晶体，称取初始原料KOH 1.00mmol(0.056g)、Ba(OH)2·8H2O1.00mmol(0.316g)、Cu 1.00mmol(0.064g)、Sb2S3 0.25mmol(0.085g)和S 2.50mmol(0.080g)放入水热釜中，再加入2.0mL聚乙二醇(PEG400)，0.5mL 85wt％水合肼，0.5mL丙二胺，将水热釜置于140℃下反应7天。产物分别用蒸馏水和无水乙醇洗涤2次，得到产率为50％的深红色块状晶体。EDX元素分析表明晶体只含K、Ba、Cu、Sb、S五种元素，且各元素含量比约为2:3:2:2:10。(见图1)。经单晶X射线衍射分析，该晶体组成式为K2Ba3Cu2Sb2S10，其中较重的K、Ba、Cu、Sb、S五种元素与EDX元素分析结果一致，属于单斜晶系，C2/m空间群，晶胞参数 α＝90°，β＝115.257(13)°，γ＝90°，Z＝2，Dc＝4.605g/cm3，晶体结构如图2所示。K 2 Ba 3 Cu 2 Sb 2 S 10 crystal, weigh the initial raw materials KOH 1.00mmol (0.056g), Ba(OH) 2 8H 2 O 1.00mmol (0.316g), Cu 1.00mmol (0.064g), Sb 2 Put S 3 0.25mmol (0.085g) and S 2.50mmol (0.080g) into a hydrothermal kettle, then add 2.0mL polyethylene glycol (PEG400), 0.5mL 85wt% hydrazine hydrate, 0.5mL propylenediamine, and water The hot pot was placed at 140°C for 7 days. The product was washed twice with distilled water and absolute ethanol respectively to obtain dark red blocky crystals with a yield of 50%. EDX elemental analysis shows that the crystal only contains K, Ba, Cu, Sb, and S, and the content ratio of each element is about 2:3:2:2:10. (see picture 1). According to single crystal X-ray diffraction analysis, the crystal composition formula is K 2 Ba 3 Cu 2 Sb 2 S 10 , among which the five heavier elements K, Ba, Cu, Sb, and S are consistent with the results of EDX element analysis, and belong to monoclinic Crystal system, C2/m space group, unit cell parameters α=90°, β=115.257(13)°, γ=90°, Z = 2, D c = 4.605 g/cm 3 , and the crystal structure is shown in Fig. 2 .
实施例3：Example 3:
K2Ba3Cu2Sb2S10晶体，称取初始原料KOH 1.30mmol(0.073g)、Ba(OH)2·8H2O1.50mmol(0.474g)、Cu 1.00mmol(0.032g)、Sb2S3 0.25mmol(0.085g)和S 2.50mmol(0.064g)放入水热釜中，再加入2.0mL聚乙二醇(PEG400)，0.5mL 85wt％水合肼，0.5mL丙二胺，将水热釜置于140℃下反应5天。产物分别用蒸馏水和无水乙醇洗涤2次，得到产率为20％的深红色块状晶体。EDX元素分析表明晶体只含K、Ba、Cu、Sb、S五种元素，且各元素含量比约为2:3:2:2:10。K 2 Ba 3 Cu 2 Sb 2 S 10 crystals, weigh the initial raw materials KOH 1.30mmol (0.073g), Ba(OH) 2 8H 2 O 1.50mmol (0.474g), Cu 1.00mmol (0.032g), Sb 2 Put S 3 0.25mmol (0.085g) and S 2.50mmol (0.064g) into a hydrothermal kettle, then add 2.0mL polyethylene glycol (PEG400), 0.5mL 85wt% hydrazine hydrate, 0.5mL propylenediamine, and water The hot pot was placed at 140° C. for 5 days. The product was washed twice with distilled water and absolute ethanol respectively to obtain dark red blocky crystals with a yield of 20%. EDX elemental analysis shows that the crystal only contains K, Ba, Cu, Sb, and S, and the content ratio of each element is about 2:3:2:2:10.
实施例4：Example 4:
Rb2Ba3Cu2Sb2S10晶体，称取初始原料RbCl 0.80mmol(0.096g)、Ba(OH)2·8H2O1.00mmol(0.316g)、Cu 0.50mmol(0.032g)、Sb2S3 0.25mmol(0.085g)和S 2.00mmol(0.064g)放入水热釜中，再加入2.0mL聚乙二醇(PEG400)，0.5mL 85wt％水合肼，0.5mL丙二胺，将水热釜置于140℃下反应5天。产物分别用蒸馏水和无水乙醇洗涤2次，得到产率为30％的深红色块状晶体。EDX元素分析表明晶体只含Rb、Ba、Cu、Sb、S五种元素，且各元素含量比约为2:3:2:2:10。Rb 2 Ba 3 Cu 2 Sb 2 S 10 crystals, weigh the initial raw materials RbCl 0.80mmol (0.096g), Ba(OH) 2 8H 2 O 1.00mmol (0.316g), Cu 0.50mmol (0.032g), Sb 2 Put S 3 0.25mmol (0.085g) and S 2.00mmol (0.064g) into a hydrothermal kettle, then add 2.0mL polyethylene glycol (PEG400), 0.5mL 85wt% hydrazine hydrate, 0.5mL propylenediamine, and water The hot pot was placed at 140° C. for 5 days. The product was washed twice with distilled water and absolute ethanol respectively to obtain dark red blocky crystals with a yield of 30%. EDX elemental analysis shows that the crystal contains only five elements: Rb, Ba, Cu, Sb, and S, and the content ratio of each element is about 2:3:2:2:10.
实施例5：Example 5:
Rb2Ba3Cu2Sb2S10晶体，称取初始原料RbCl 1.00mmol(0.120g)、Ba(OH)2·8H2O1.00mmol(0.316g)、Cu 1.00mmol(0.064g)、Sb2S3 0.25mmol(0.085g)和S 2.50mmol(0.080g)放入水热釜中，再加入2.0mL聚乙二醇(PEG400)，0.5mL 85wt％水合肼，0.5mL丙二胺，将水热釜置于140℃下反应7天。产物分别用蒸馏水和无水乙醇洗涤2次，得到产率为50％的深红色块状晶体。EDX元素分析表明晶体只含Rb、Ba、Cu、Sb、S五种元素，且各元素含量比约为2:3:2:2:10。(见图1)。经单晶X射线衍射分析，该晶体组成式为Rb2Ba3Cu2Sb2S10，其中较重的Rb、Ba、Cu、Sb、S五种元素与EDX元素分析结果一致，属于单斜晶系，C2/m空间群，晶胞参数 α＝90°，β＝115.992(11)°，γ＝90°，Z＝2，Dc＝4.332g/cm3，晶体结构如图2所示。对晶体粉末进行XRD测试,结果如图3所示。UV-vis图谱测得半导体材料能隙为1.7eV(见图4)，模拟太阳光下光响应电流为4μA/cm2(见图5)。For Rb 2 Ba 3 Cu 2 Sb 2 S 10 crystal, weigh the initial raw materials RbCl 1.00mmol (0.120g), Ba(OH) 2 8H 2 O 1.00mmol (0.316g), Cu 1.00mmol (0.064g), Sb 2 Put S 3 0.25mmol (0.085g) and S 2.50mmol (0.080g) into a hydrothermal kettle, then add 2.0mL polyethylene glycol (PEG400), 0.5mL 85wt% hydrazine hydrate, 0.5mL propylenediamine, and water The hot pot was placed at 140°C for 7 days. The product was washed twice with distilled water and absolute ethanol respectively to obtain dark red blocky crystals with a yield of 50%. EDX elemental analysis shows that the crystal contains only five elements: Rb, Ba, Cu, Sb, and S, and the content ratio of each element is about 2:3:2:2:10. (see picture 1). According to single crystal X-ray diffraction analysis, the crystal composition formula is Rb 2 Ba 3 Cu 2 Sb 2 S 10 , among which the five heavier elements Rb, Ba, Cu, Sb, and S are consistent with the results of EDX element analysis, and belong to monoclinic Crystal system, C2/m space group, unit cell parameters α=90°, β=115.992(11)°, γ=90°, Z = 2, D c = 4.332 g/cm 3 , and the crystal structure is shown in Fig. 2 . The crystal powder was tested by XRD, and the results are shown in Figure 3. The energy gap of the semiconductor material measured by UV-vis spectrum is 1.7eV (see Figure 4), and the photoresponse current under simulated sunlight is 4μA/cm 2 (see Figure 5).
实施例6：Embodiment 6:
Rb2Ba3Cu2Sb2S10晶体，称取初始原料RbCl 1.30mmol(0.156g)、Ba(OH)2·8H2O1.00mmol(0.316g)、Cu 1.00mmol(0.064g)、Sb2S3 0.25mmol(0.085g)和S 2.50mmol(0.080g)放入水热釜中，再加入2.0mL聚乙二醇(PEG400)，1.0mL 85wt％水合肼，将水热釜置于140℃下反应7天。产物分别用蒸馏水和无水乙醇洗涤2次，得到产率为30％的深红色块状晶体。EDX元素分析表明晶体只含Rb、Ba、Cu、Sb、S五种元素，且各元素含量比约为2:3:2:2:10。Rb 2 Ba 3 Cu 2 Sb 2 S 10 crystals, weigh the initial raw materials RbCl 1.30mmol (0.156g), Ba(OH) 2 8H 2 O 1.00mmol (0.316g), Cu 1.00mmol (0.064g), Sb 2 Put S 3 0.25mmol (0.085g) and S 2.50mmol (0.080g) into a hydrothermal kettle, then add 2.0mL polyethylene glycol (PEG400), 1.0mL 85wt% hydrazine hydrate, and place the hydrothermal kettle at 140°C Under the reaction for 7 days. The product was washed twice with distilled water and absolute ethanol respectively to obtain dark red blocky crystals with a yield of 30%. EDX elemental analysis shows that the crystal contains only five elements: Rb, Ba, Cu, Sb, and S, and the content ratio of each element is about 2:3:2:2:10.
实施例7：Embodiment 7:
Cs2Ba3Cu2Sb2S10晶体，称取初始原料CsOH·8H2O 50％水溶液0.536g(0.80mmol)、Ba(OH)2·8H2O 1.00mmol(0.316g)、Cu 0.50mmol(0.032g)、Sb2S3 0.25mmol(0.085g)和S2.00mmol(0.064g)放入水热釜中，再加入2.0mL聚乙二醇(PEG400)，0.5mL 85wt％水合肼，0.5mL丙二胺，将水热釜置于140℃下反应5天。产物分别用蒸馏水和无水乙醇洗涤2次，得到产率为10％的深红色块状晶体。EDX元素分析表明晶体只含Cs、Ba、Cu、Sb、S五种元素，且各元素含量比约为2:3:2:2:10。Cs 2 Ba 3 Cu 2 Sb 2 S 10 crystal, weigh the initial raw materials CsOH·8H 2 O 50% aqueous solution 0.536g (0.80mmol), Ba(OH) 2 ·8H 2 O 1.00mmol (0.316g), Cu 0.50mmol (0.032g), Sb 2 S 3 0.25mmol (0.085g) and S2.00mmol (0.064g) were put into a hydrothermal kettle, then added 2.0mL polyethylene glycol (PEG400), 0.5mL 85wt% hydrazine hydrate, 0.5 mL of propylenediamine was placed in a hydrothermal kettle at 140°C for 5 days. The product was washed twice with distilled water and absolute ethanol, respectively, to obtain dark red blocky crystals with a yield of 10%. EDX elemental analysis shows that the crystal contains only five elements: Cs, Ba, Cu, Sb, and S, and the content ratio of each element is about 2:3:2:2:10.
实施例8：Embodiment 8:
Cs2Ba3Cu2Sb2S10晶体，Cs2Ba3Cu2Sb2S10晶体，称取初始原料CsOH·8H2O 50％水溶液0.670g(0.10mmol)、Ba(OH)2·8H2O 1.00mmol(0.316g)、Cu 1.00mmol(0.064g)、Sb2S30.25mmol(0.085g)和S 2.50mmol(0.080g)放入水热釜中，再加入2.0mL聚乙二醇(PEG400)，0.5mL 85wt％水合肼，0.5mL丙二胺，将水热釜置于140℃下反应7天。产物分别用蒸馏水和无水乙醇洗涤2次，得到产率为40％的深红色块状晶体。EDX元素分析表明晶体只含Cs、Ba、Cu、Sb、S五种元素，且各元素含量比约为2:3:2:2:10。(见图1)。经单晶X射线衍射分析，该晶体组成式为Cs2Ba3Cu2Sb2S10，其中较重的Cs、Ba、Cu、Sb、S五种元素与EDX元素分析结果一致，属于单斜晶系，C2/m空间群，晶胞参数 α＝90°，β＝116.514(15)°，γ＝90°， Z＝2，Dc＝4.524g/cm3，晶体结构如图2所示。Cs 2 Ba 3 Cu 2 Sb 2 S 10 crystal, Cs 2 Ba 3 Cu 2 Sb 2 S 10 crystal, weigh 0.670 g (0.10 mmol) of the initial raw material CsOH·8H 2 O 50% aqueous solution, Ba(OH) 2 ·8H 2 O 1.00mmol (0.316g), Cu 1.00mmol (0.064g), Sb 2 S 3 0.25mmol (0.085g) and S 2.50mmol (0.080g) were placed in a hydrothermal kettle, and then 2.0mL polyethylene glycol was added (PEG400), 0.5mL 85wt% hydrazine hydrate, and 0.5mL propylenediamine were placed in a hydrothermal kettle at 140° C. for 7 days. The product was washed twice with distilled water and absolute ethanol respectively to obtain a deep red blocky crystal with a yield of 40%. EDX elemental analysis shows that the crystal contains only five elements: Cs, Ba, Cu, Sb, and S, and the content ratio of each element is about 2:3:2:2:10. (see picture 1). According to single crystal X-ray diffraction analysis, the crystal composition formula is Cs 2 Ba 3 Cu 2 Sb 2 S 10 , among which the five heavier elements of Cs, Ba, Cu, Sb, and S are consistent with the results of EDX element analysis, and belong to monoclinic Crystal system, C2/m space group, unit cell parameters α=90°, β=116.514(15)°, γ=90°, Z = 2, D c = 4.524 g/cm 3 , and the crystal structure is shown in Fig. 2 .
实施例9：Embodiment 9:
Cs2Ba3Cu2Sb2S10晶体，称取初始原料CsOH·8H2O 50％水溶液0.871g(0.13mmol)、Ba(OH)2·8H2O 1.50mmol(0.474g)、Cu 1.00mmol(0.032g)、Sb2S3 0.25mmol(0.085g)和S2.50mmol(0.064g)放入水热釜中，再加入2.0mL聚乙二醇(PEG400)，0.5mL 85wt％水合肼，0.5mL丙二胺，将水热釜置于140℃下反应7天。产物分别用蒸馏水和无水乙醇洗涤2次，得到产率为20％的深红色块状晶体。EDX元素分析表明晶体只含Cs、Ba、Cu、Sb、S五种元素，且各元素含量比约为2:3:2:2:10。Cs 2 Ba 3 Cu 2 Sb 2 S 10 crystal, weigh the initial raw material CsOH·8H 2 O 50% aqueous solution 0.871g (0.13mmol), Ba(OH) 2 ·8H 2 O 1.50mmol (0.474g), Cu 1.00mmol (0.032g), Sb 2 S 3 0.25mmol (0.085g) and S2.50mmol (0.064g) were put into a hydrothermal kettle, then added 2.0mL polyethylene glycol (PEG400), 0.5mL 85wt% hydrazine hydrate, 0.5 mL of propylenediamine was placed in a hydrothermal kettle at 140°C for 7 days. The product was washed twice with distilled water and absolute ethanol respectively to obtain dark red blocky crystals with a yield of 20%. EDX elemental analysis shows that the crystal contains only five elements: Cs, Ba, Cu, Sb, and S, and the content ratio of each element is about 2:3:2:2:10.
以上所述的实施例只是本发明的一种较佳的方案，然其并非用以限制本发明，凡采取等同替换或等效变换的方式所获得的技术方案，均落在本发明的保护范围内。The above-described embodiment is only a preferred solution of the present invention, but it is not intended to limit the present invention, and all technical solutions obtained by means of equivalent replacement or equivalent transformation all fall within the protection scope of the present invention Inside.
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