CN105801877A - Organic/inorganic hybridized cuprous iodine anion high-polymeric chain-based semiconductor material - Google Patents
Organic/inorganic hybridized cuprous iodine anion high-polymeric chain-based semiconductor material Download PDFInfo
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Abstract
The invention discloses an organic/inorganic hybridized cuprous iodine anion high-polymeric chain-based semiconductor material and a preparation method thereof. The molecular structural formula of the organic/inorganic hybridized wide bandgap semiconductor material is (MV)n(Cu2I4)n, wherein in the formula, MV is organic cation methyl viologen with two units of positive charges; n is the number of repetitive units of a polymer structure; the (Cu2I4)n high-polymeric anion in the material is of a linear chain-shaped structure. Through coordination polymerization reaction of cuprous iodide and the solution of methyl viologen iodide, the organic/inorganic hybridized semiconductor material which is good in semiconductor property and thermal stability can be conveniently and cheaply prepared, and the material is moderate in bandgap width and good in thermal stability, and can be applied to the technical field of electronic materials.
Description
Technical field
The present invention relates to technical field of semiconductor, relate to inorganic polymer material and organic-inorganic hybrid material field, particularly relate to iodide base semiconductor material field.
Background technology
Electronic technology is one of basis of the modernization of science technology, is also a marked feature of modern science and technology.Currently, electronic technology has penetrated into the every field of national economy, and the rise of electronics industry also brings the extensive and deep technological innovation of national economy.What play a major role in electronic technology is the element made by heart semi-conducting material of electronic equipment.From this, semi-conducting material is just the basis of electronics industry, it is also the most important raw material of electronics industry.Review history, from mid-term in last century, the development of the discovery of silicon materials and the integrated circuit based on silicon at the fifties initial stage, result in electronics industry revolutionary character tide.Now, computer, the Internet, Internet of Things, robotics development make rapid progress, and these technology are also inseparable with the development of modern microelectronic technology, are also basic with developing into of semiconductor material technology.
The effort through nearly half a century of the Semiconductor Materials Industry of China develops, have been provided with certain basis, particularly after reform and opening-up, China's semi-conducting material obtains significantly development, except the demand substantially meeting domestic market, even have begun to some materials and stepped into international market.But carefully it is found that the situation of China's semiconductor industry chain is after investigation, the technology application of downstream and market development ability are relatively strong, and it is in the innovative design of upstream extremity and processing and manufacturing level is still more weak；Especially the level that the key issue highlighted in industrial chain is then material development still has much room for improvement, and needs badly " seven cun " place being held in the hand in the middle of this Ye Shi China semiconductor industry development.Therefore, research and develop semi-conducting material energetically, promote the progress of semiconductor industry and electronic technology to be of great immediate significance.
The invention of 20 middle of century, monocrystal silicon and semiconductor transistor and succeeding in developing of silicon integrated circuit thereof, result in electronics industry revolution；Silicon fiber material and the invention of GaAs laser instrument, promoted Fibre Optical Communication Technology to develop rapidly and gradually formed new high-tech industry, having made the mankind enter the information age beginning of the seventies in last century.The proposition of superlattices concept and semiconductor superlattice thereof, the succeeding in developing of quantum-well materials, revolutionize the design philosophy of photoelectric device, make the design of semiconductor device develop into " energy band engineering " with manufacturing from " impurity engineering ".The development of nanoscale science and technology and application, by making the mankind can control, handle and manufacture powerful new device and circuit from atom, molecule or nanoscale levels, will thoroughly change the life style of people.In the semi-conducting material that component and performance are innovated, countries in the world have also all put into substantial amounts of research and development strength, also obtain considerable progress.As far back as 1999, China just succeeded in developing the InGaAs interband QCL of 980nm；At the beginning of 2000, the quasi-continuous output of the single semiconductor laser of THO's report is more than 10 watts；Along with the P type doping of GaN material in 1993 breaks through, GaN base material becomes the study hotspot of blue green light luminescent material, thus bring with the LED solid-state semiconductor being representative illuminate flourish；And recently, researcher, by utilizing the lead halide base semiconductor of perovskite structure, constantly makes a breakthrough in novel solar battery research and development, current energy conversion efficiency has matched in excellence or beauty silicon-based semiconductor, presents huge potentiality to be exploited.
In recent years, in order to solve the increasingly serious energy and environmental problem, people have invested sight in the development and utilization of new forms of energy.In various new energy technologies, photovoltaic generation is undoubtedly one of most promising direction.Although traditional silica-based solar cell achieves industrialization, there is comparatively ripe market, but its cost performance also cannot be competed with traditional energy mutually, and pollution and the energy consumption problem in manufacture process have impact on its extensive use.Therefore, research and development high efficiency, low cost novel solar battery very necessary.In numerous novel solar batteries, perovskite thin film solaode is shown one's talent for nearly 2 years, has attracted the concern of numerous researcher, also it is chosen as one of ten big science breakthroughs in 2013 (Wei Jing, Zhao Qing, Li Heng by " Science ", executing Cheng Long, build up the Army in field, Cao Guozhong, Yu great Peng, perovskite solaode: the new hope of photovoltaic art, Chinese science: science of technology, 2014,44 (8), 801-821.).The electricity conversion of perovskite thin film solaode brings up to rapidly 16.2% (by the end of end of the year 2013) through certification from 3.8% within the time of 5 years, the novel thin film solar cell such as DSSC, organic solar batteries is got rid of after one's death, and this also has benefited from the specific absorbance that such new material is high.As can be seen here, emerging in large numbers of novel semiconductor material, often bring the innovation of photoelectron technology simultaneously.But for technology application demand now, existing alternative semi-conducting material is still inadequate, still has very big innovation research and development space and needs.Therefore, the compound semiconductor materials of the novel component that development of new is cheap has great national strategy meaning and important actual application value.
Summary of the invention
Cuprous iodine anion high poly chain base semiconductor material that it is an object of the invention to provide a kind of organic inorganic hybridization and preparation method thereof.Solution generation coordination poly-merization by Hydro-Giene (Water Science). Yu methyl viologen iodide, convenient and prepared semiconducting behavior and the good organic inorganic hybridization semi-conducting material of thermal stability at a low price, its energy gap is moderate, Heat stability is good, can be applied to photoelectron material technical field.
One of technical scheme, is to provide a kind of new organic inorganic hybridization semi-conducting material, the solution generation coordination poly-merization of Hydro-Giene (Water Science). Yu methyl viologen iodide obtain, and its molecular structural formula is (MV)n(Cu2I4)n, in formula, MV is the organic cation methyl viologen with two unit positive charges, and n is the number of repeat unit of Polymer Structure, the similar degree of polymerization.
Described organic cation methyl viologen, is 4, two N in 4 '-second bipyridine methylate formed cation, two unit positive charges of each cation band, its molecular structure such as formula (I):
Described semi-conducting material is tetragonal crystal system, P42/ mnm space group, cell parameter is α=90.00 °, β=90.00 °, γ=90.00 °,Z=2, DC=2.787g/cm3, the crystal color of material is black；This semiconductor material structures shows as ion-type organic-inorganic hybrid structure, and its cationic is the isolated purpurine cation with two unit positive charges, and anion is then (the Cu of the straight line chain structure of cuprous ion and iodide ion polymerization composition2I4)nCuprous iodine anion, two unit negative charge of each polymerized unit band, total reaches neutral charge；In the polymer anion of this material, cuprous ion adopts CuI4Tetrahedral coordination mode, and each iodide ion adopts μ2Two cuprous ions that the connection of abutment coordination mode is adjacent, Cu-Cu spacing isFrom the c-axis direction of its structure cell, this anion linear architectural feature of high poly chain；The molecular structure of this semi-conducting material such as formula (II):
Described semi-conducting material is applied to medium bandgap semiconductor material, and this material energy gap is 1.79eV, can strongly absorb photon energy more than the visible ray of this threshold value and ultraviolet light, and maximum absorption peak is positioned at 530nm wavelength place.
The two of technical scheme, are to provide cuprous iodine anion high poly chain base semiconductor material (MV) of a kind of organic inorganic hybridizationn(Cu2I4)nPreparation method.This preparation method is to be obtained by the solution generation complexation reaction of Hydro-Giene (Water Science). and methyl viologen iodide, finally realizes so that precipitation obtains the product of crystal powder.Its specific embodiments is divided into three steps:
(1) under room temperature, Hydro-Giene (Water Science). pressed powder is dissolved in acetonitrile, obtains settled solution A；
(2) under room temperature, the solid of methyl viologen iodide is dissolved in water, obtains settled solution B；
(3) described solution B is added in solution A, form muddiness at once, continuation stirring reaction half an hour after having fed in raw material, form a large amount of crystalline product, filter and precipitate out crystal, wash twice respectively with water and ethanol again, vacuum drying, finally obtain a large amount of black color crystal and be described hybrid material target product.
In preparation method of the present invention, the two reactant Hydro-Giene (Water Science).: the mol ratio of methyl viologen iodide is 2: 1.
First beneficial effects of the present invention is cuprous iodine anion high poly chain base semiconductor material (MV) of the organic inorganic hybridization providedn(Cu2I4)n, the organic cation wherein introduced is methyl viologen MV, and purpurine cation has typical charge transfer characteristic, and itself and cuprous iodine anion form organic-inorganic hybrid structure and be conducive to the jumping type of carrier to transmit；On the other hand, the inorganic anion in this material is the cuprous iodine anion (Cu of high poly chain structure2I4)n, wherein cuprous ion adopts CuI4Tetrahedral coordination mode, and each iodide ion adopts μ2Two cuprous ions that the connection of abutment coordination mode is adjacent, thus the cuprous and iodide ion alternately connection that electronegativity is more weak, be formed with the inorganic high poly chain structure of the linear being beneficial to conduction；Actual this material of display of measuring has the energy gap of 1.79 electron-volts, thus this material is good medium bandgap semiconductor material.This organic inorganic hybridization semi-conducting material had both possessed advantage that is cheap and that be prone to purification, and had good heat stability, and the application further for Hybrid semiconductor material provides technical support.
Beneficial effects of the present invention, next to that prepare cuprous iodine anion high poly chain base semiconductor material (MV) of organic inorganic hybridizationn(Cu2I4)nMethod, there is simple process, device therefor is simple, and production cost is low, it is possible to obtain having the advantage such as product of significantly high productivity in a short period of time.
Accompanying drawing explanation
Fig. 1. cuprous iodine anion high poly chain base semiconductor material (MV) of organic inorganic hybridizationn(Cu2I4)nThe crystallography separate unit mono-crystalline structures figure of molecule.
Fig. 2. cuprous iodine anion high poly chain base semiconductor material (MV) of organic inorganic hybridizationn(Cu2I4)nThe structure chart of the poly-coiled strand of cuprous iodine anion height in molecule.
Fig. 3. cuprous iodine anion high poly chain base semiconductor material (MV) of organic inorganic hybridizationn(Cu2I4)nMolecule is in unit cell and the accumulation graph of peripheral space.
Fig. 4. cuprous iodine anion high poly chain base semiconductor material (MV) of organic inorganic hybridizationn(Cu2I4)nUltraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 5. cuprous iodine anion high poly chain base semiconductor material (MV) of organic inorganic hybridizationn(Cu2I4)nTG-DTA (TG-DSC) analyze curve, abscissa represents that temperature, left side vertical coordinate represent percetage by weight, and right side vertical coordinate represents heat.
Detailed description of the invention
The process that realizes of the present invention and the performance of material are illustrated by embodiment:
Embodiment 1
Cuprous iodine anion high poly chain base semiconductor material (MV) of substantial amounts of organic inorganic hybridizationn(Cu2I4)nThe preparation of crystal prototype: the Hydro-Giene (Water Science). weighing 0.191g (1mmol) is dissolved in 30 milliliters of acetonitriles and obtains settled solution A, the methyl viologen iodide weighing 0.222g (0.5mmol) are dissolved in 5 milliliters of water and obtain settled solution B；Then, above-mentioned solution B is added in solution A, form muddiness at once, after having fed in raw material, continuation stirring reaction half an hour, forms a large amount of crystalline product, filters and precipitates out crystal, wash twice respectively with water and ethanol again, vacuum drying, finally obtains a large amount of black crystals and is described hybrid material target product, and productivity is more than 80%.
Embodiment 2
Cuprous iodine anion high poly chain base semiconductor material (MV) of synthesis organic inorganic hybridizationn(Cu2I4)nMonocrystalline: weigh 19mg (0.1mmol) Hydro-Giene (Water Science). be dissolved in 5 milliliters of acetonitriles settled solution A, weigh 22mg (0.05mmol) methyl viologen iodide be dissolved in 5 milliliters of water settled solution B；Then, first solution B is placed in test tube, then is slowly added in test tube by solution A to be at the upper strata of solution B, stand after test tube sealing, have a large amount of black bulk crystals to precipitate out after a few days.The black bulk crystals selecting a 0.18mm*0.12mm*0.10mm size is tested for x-ray crystal structure.The structure chart of the crystallography separate unit of this compound is shown graphically in the attached figures 1, and the structure chart of its cuprous iodine anion high poly chain and corresponding counter cation methyl viologen is shown graphically in the attached figures 2, and its structure cell packed structures is illustrated in accompanying drawing 3.
Cuprous iodine anion high poly chain base semiconductor material (MV) to organic inorganic hybridizationn(Cu2I4)nPure phase crystal prototype carried out some row performance tests.Material crystals of the present invention has been carried out UV-Vis DRS spectrum test, result shows that the energy gap of this material is 1.79eV, can strongly absorb photon energy more than the visible ray of this threshold value and ultraviolet light, maximum absorption peak is positioned at 530nm wavelength place, and concrete ultraviolet-visible spectrum is as shown in Figure 4.This invention material has carried out hot analysis, and thermogravimetric-means of differential scanning calorimetry (TG-DSC) test shows that this material has good stability, as shown in Figure 5.Visible, this organic-inorganic hybrid material is good medium bandgap semiconductor material, and this material had both possessed advantage that is cheap and that be prone to purification, also had good heat stability simultaneously.The application further that this invention is Hybrid semiconductor material provides technical support.
Claims (4)
1. the cuprous iodine anion high poly chain base semiconductor material of an organic inorganic hybridization, it is characterised in that: the structural formula of semi-conducting material is (MV)n(Cu2I4)n, in formula, MV is the organic cation methyl viologen with two unit positive charges, and n is the number of repeat unit of Polymer Structure；Described organic cation methyl viologen, is 4, two N in 4 '-second bipyridine methylate formed cation, two unit positive charges of each cation band, its structure such as formula (I):
Described semi-conducting material is tetragonal crystal system, P42/ mnm space group, cell parameter is α=90.00 °, β=90.00 °, γ=90.00 °,Z=2, DC=2.787g/cm3, the crystal color of material is black；This semiconductor material structures shows as ion-type organic-inorganic hybrid structure, and its cationic is the isolated purpurine cation with two unit positive charges, and anion is then (the Cu of the straight line chain structure of cuprous ion and iodide ion polymerization composition2I4)nCuprous iodine anion, two unit negative charge of each polymerized unit band, total reaches neutral charge；In the polymer anion of this material, cuprous ion adopts CuI4Tetrahedral coordination mode, and each iodide ion adopts μ2Two cuprous ions that the connection of abutment coordination mode is adjacent, Cu-Cu spacing isFrom the c-axis direction of its structure cell, this anion linear architectural feature of high poly chain；The molecular structure of this semi-conducting material such as formula (II):
2. the preparation method of organic inorganic hybridization semi-conducting material according to claim 1, its method comprises the following steps:
(1) under room temperature, Hydro-Giene (Water Science). pressed powder is dissolved in acetonitrile, obtains settled solution A；
(2) under room temperature, the solid of methyl viologen iodide is dissolved in water, obtains settled solution B；
(3) described solution B is added in solution A, form muddiness at once, continuation stirring reaction half an hour after having fed in raw material, form a large amount of crystalline product, filter and precipitate out crystal, wash twice respectively with water and ethanol again, vacuum drying, finally obtain a large amount of black color crystal and be described hybrid material target product.
3. the preparation method of organic inorganic hybridization semi-conducting material according to claim 2, it is characterised in that: the two reactant Hydro-Giene (Water Science).: the mol ratio of methyl viologen iodide is 2: 1.
4. the application of organic inorganic hybridization semi-conducting material according to claim 1, it is characterized in that described semi-conducting material energy gap is 1.79eV, photon energy can be absorbed more than the visible ray of this threshold value and ultraviolet light, maximum absorption peak is positioned at 530nm wavelength place, can apply as the semi-conducting material of medium energy gap.
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| CN110552065A (en) * | 2019-09-19 | 2019-12-10 | 华中科技大学 | Chain-like iodide material and preparation and application thereof |
| CN115074834A (en) * | 2022-05-13 | 2022-09-20 | 陕西师范大学 | Monovalent copper-based perovskite material and preparation method thereof |
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