CN101565855B - Method for preparing silicon nanocrystal superlattice structure based on co-evaporation method - Google Patents
Method for preparing silicon nanocrystal superlattice structure based on co-evaporation method Download PDFInfo
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- CN101565855B CN101565855B CN200810104757XA CN200810104757A CN101565855B CN 101565855 B CN101565855 B CN 101565855B CN 200810104757X A CN200810104757X A CN 200810104757XA CN 200810104757 A CN200810104757 A CN 200810104757A CN 101565855 B CN101565855 B CN 101565855B
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Abstract
The invention discloses a method for preparing a silicon nanocrystal superlattice structure based on a co-evaporation method. The method is mainly characterized in that a method prepares laminated silicon quantum dots on a silicon substrate by utilizing electron beam evaporation equipment, and comprises the main steps of: growing a silicon dioxide insulation layer through thermal oxidation on the silicon substrate; using an electron beam evaporation method to evaporate a mixture of silicon solid particles and hafnium oxide solid particles to the insulation layer; and performing high-temperature thermal annealing. The size of quantum dot particles prepared by the method is about between 3 and 6 nm; and the quantum dot particles can be used for the production of single electron devices or single electron memories, particularly for the production of solar batteries and the like. The method has the advantages of few process steps, simplicity, stability, reliability, easy mass production and the compatibility with the prior microelectronic process.
Description
Technical field
The invention belongs to technical field of nano-processing, particularly a kind of preparation method with nanocrystal superstructure film.
Background technology
Along with the rapid increase of world population, fossil energy is exhausted gradually, and is increasing to the demand of other non-mineral energy.Particularly after 20th century, broke out oil crisis the seventies, the utilization of sun power obtained very big development.
Since Bell Laboratory in 1954 was reported first commercial Si solar cell, various solar cells were come out one after another.By the continuous development of recent decades, solar cell is from the thin-film solar cells of the monocrystaline silicon solar cell of the first-generation, the s-generation high performance solar batteries of the third generation till now, and its cost of manufacture progressively reduces, and efficiency of conversion improves constantly.Wherein first-generation s-generation solar cell is used on market; Third generation solar cell will make full use of nanotechnology, still be in the development at present.
The nano-crystalline thin film solar cell is to belong to third generation solar cell.Nanocrystalline typical sizes is 1 to 10 nanometer, comprises several to dozens of atoms, because the motion of Charge carrier is subjected to three-dimensional restriction at quantum dot, energy generation quantization.Quantum dot has numerous characteristics, in the utilization of third generation solar cell, it will utilize this characteristic of transformable bandwidth, reach absorption to the sunlight bands of a spectrum, but not single wavelength, this makes quantum dot solar cell can improve optoelectronic transformation efficiency greatly, compare with present most popular polysilicon solar cell, production energy consumption can reduce 20%, and photoelectric efficiency can increase more than 50% to 1 times, and has reduced expensive Master Cost greatly.
At present the nanocrystalline method of preparation have multiple, such as plasma-reinforced chemical vapor deposition method (PECVD), low-pressure chemical vapor phase deposition (LPCVD) method, ion implantation Si to SiO
2In the method for going, but these methods all can not the nanocrystalline superstructure of mass preparation.Have only a kind of method to prepare nanocrystalline superstructure-reaction SiO method of evaporation in the world, this method is evaporation one deck SiO, is reoxidised into SiO
2, so be concatenated to form nanocrystalline superlattice; This method is very numerous and diverse, and the cycle is long, only is suitable for research and uses and be unsuitable for large-scale production in batches.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing superlattice structure of silicon nanocrystal, to be used for third generation solar cell.
The present invention proposes a kind ofly to be equipped with the method for superlattice structure of silicon nanocrystal based on steaming legal system altogether, comprises the steps:
One, growthing silica layer on substrate;
Two, the mixture with silicon grain and oxide particle is evaporated on the described silicon dioxide layer;
Three, place annealing furnace to carry out high-temperature thermal annealing in above-mentioned sample.
Further, wherein the described substrate of step 1 is a silicon chip, or is the SOI substrate, or is steel disc.
Further, described oxide particle is the hafnium oxide particle, or is the aluminium sesquioxide particle, or is the silicon monoxide particle, or is zirconium dioxide particle, or is the Manganse Dioxide particle, or is the cobalt dioxide particle.
Further, the silicon-dioxide of being grown on described silicon chip or the SOI substrate is thermal oxide growth, and the growth pattern on the described steel disc is plasma-reinforced chemical vapor deposition method or electron beam evaporation silicon-dioxide.
Further, the described electron beam evaporation that is evaporated to.
Further, the used particle diameter size range of described electron beam evaporation is 1 millimeter to 6 millimeters.
Further, the described high-temperature thermal annealing that is annealed under nitrogen protection atmosphere of step 3 wherein.
The present invention is with the Si particle of certain size and hafnium oxide particle (or other oxide particle, see above-mentioned) uniform mixing by a certain percentage, such two kinds of particulate matter uniform mixing.During electron beam evaporation, the small electron beam that electron beam gun sends is got on these particles, evaporates another particle of particle revaporization, can form multilayered structure like this; It is nanocrystalline to understand formation after annealed, forms nanocrystalline superstructure.
Because the method institute employing equipment for preparing superlattice structure of silicon nanocrystal provided by the present invention all comes from traditional semiconductor fabrication process, so it is easy to compatiblely mutually with existing microelectronic technique, is suitable for large-scale mass production; Employed material of present method such as oxide compound high dielectric constant materials such as Si, SiO, hafnium oxide are employed material in the microelectronic technique, and are therefore with low cost, with the compatible coupling of microelectronic technique.Under the situation that does not need extra investment, can use existing mature equipment, technology and material, accomplish scale production.
Description of drawings
Fig. 1 is that thermooxidizing forms one deck SiO on the silicon substrate
2(step 1 of corresponding " embodiment " part);
Fig. 2 is mixtures such as electron beam evaporation Si particle and hafnium oxide particle (step 2 of corresponding " embodiment " part);
Fig. 3 is the nanocrystalline superstructure of Si that annealing forms under nitrogen atmosphere (step 3 of corresponding " embodiment " part);
Fig. 4 is the images of transmissive electron microscope that adopts manufactured samples of the present invention, can see among the figure that the Si that has lattice fringe is nanocrystalline;
Fig. 5 is the images of transmissive electron microscope that adopts manufactured samples of the present invention, can see rhythmo structure in layer among the figure, i.e. superstructure.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
The quick-reading flow sheets of invention is as follows:
Step 1, as shown in Figure 1 is by thermal oxide growth technology growthing silica layer 102 on silicon substrate 101;
Step 2, is as shown in Figure 2 plated one deck silicon and hafnium oxide mixture film 201 by the mode of electron beam evaporation on silicon dioxide layer 102;
Step 3, is as shown in Figure 3 carried out high-temperature thermal annealing with sample under nitrogen protection atmosphere, form quantum-dot superlattice structure 301.
Further specify detailed process method of the present invention and step below, wherein:
Adopt 2 cun silicon chips in p type, (100) crystal orientation to do substrate, the thick 525um of this substrate, resistivity is 2-3 Ω cm.Concrete processing step is as follows:
(1) with silicon chip 900 ℃ of oxidations 10 minutes in the rapid thermal oxidation stove, growth compact oxide; Aerating oxygen during thermooxidizing can also can be with the way of hot oxygen with the way of wet oxygen.This depends on the thickness of thermal oxide layer.
(2) mixture of silicon and hafnium oxide on the electron beam evaporation.Wherein, mixture is by the silicon grain of 3.5 grams and the hafnium oxide granulometric composition of 2.5 grams, and evaporation V-bar is
This ratio is learnt through calculating.Form the Si quantum dot, must form the hafnium oxide layer of rich Si, the atomic ratio of Si and hafnium (Hf) will reach 35%; Only in this way move back for the time just can have Si nanocrystalline by crystallization-nucleation-growth-formation.
(3) high-temperature thermal annealing was annealed 45 minutes for 1050 ℃.It is enough high that the selection of temperature is wanted, and the time is wanted sufficiently long, otherwise can't form quantum dot.The mobile growth needs certain energy of Si atom, temperature enough Gao Shineng provide abundant energy, in considerable time, can be enriched to grow into together nanocrystalline.
Fig. 4, Fig. 5 are by the viewed result of high resolving power transmission electron microscope.Fig. 4 is the transmission electron microscope picture of scale when being 10nm, can see lattice fringe in the drawings, and these lattice fringes are that this is the strong evidence that the proof quantum dot forms because nanocrystalline crystalline network forms the diffraction of electronics.Fig. 5 then is the transmission electron microscope picture of scale when being 50nm, can see laminate structure in the drawings.This laminate structure forms by being mingled with the Si quantum dot in the hafnium oxide layer exactly, and this structure is referred to as superstructure.The result of Fig. 4 and Fig. 5 is combined, just be referred to as quantum-dot superlattice structure.It is the basic material structure of third generation solar cell, is one of core texture.Such structure does not also have other method to occur at present except forming with reaction SiO method of evaporating in the world.Our all technologies and material are all compatible mutually with the microelectronic technique of standard, can utilize fully sophisticated microelectronics reach fast, in batches, high-quality production, for its application in third generation solar cell is laid a good foundation.
The above; only be the embodiment among the present invention, but protection scope of the present invention is not limited thereto, anyly is familiar with the people of this technology in technical scope disclosed in this invention; the conversion that can expect easily or replacement all should be encompassed in of the present invention comprising within the scope.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (7)
1. one kind is equipped with the method for superlattice structure of silicon nanocrystal based on steaming legal system altogether, it is characterized in that, comprises the steps:
One, growthing silica layer on substrate;
Two, the mixture with silicon grain and oxide particle is evaporated on the described silicon dioxide layer;
Three, place annealing furnace to carry out high-temperature thermal annealing above-mentioned substrate of having grown silicon dioxide layer and silicon grain and oxide particle mixture.
2. method according to claim 1 is characterized in that, wherein the described substrate of step 1 is a silicon chip, or is the SOI substrate, or is steel disc.
3. method according to claim 1 is characterized in that, described oxide particle is the hafnium oxide particle, or is the aluminium sesquioxide particle, or is the silicon monoxide particle, or is zirconium dioxide particle, or is the Manganse Dioxide particle, or is the cobalt dioxide particle.
4. method according to claim 2 is characterized in that, the silicon-dioxide of being grown on described silicon chip or the SOI substrate is thermal oxide growth, and the growth pattern on the described steel disc is plasma-reinforced chemical vapor deposition method or electron beam evaporation silicon-dioxide.
5. method according to claim 1 is characterized in that, the described electron beam evaporation that is evaporated to.
6. according to claim 4 or 5 described methods, it is characterized in that the used particle diameter size range of described electron beam evaporation is 1 millimeter to 6 millimeters.
7. method according to claim 1 is characterized in that, wherein the described high-temperature thermal annealing that is annealed under nitrogen protection atmosphere of step 3.
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| CN200810104757XA CN101565855B (en) | 2008-04-23 | 2008-04-23 | Method for preparing silicon nanocrystal superlattice structure based on co-evaporation method |
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| CN101565855B true CN101565855B (en) | 2011-06-29 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974883A (en) * | 2006-11-30 | 2007-06-06 | 复旦大学 | Prepn process of nanometer silicon crystal |
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| CN1974883A (en) * | 2006-11-30 | 2007-06-06 | 复旦大学 | Prepn process of nanometer silicon crystal |
Non-Patent Citations (2)
| Title |
|---|
| J.A.Moreno等.Size dependence of refractive index of Si nanoclusters embedded in SiO2.《JOURNAL OF APPLIED PHYSICS》.2005,第98卷013523-1-4. * |
| Sangjin Park等.Multibit memories using a structure of SiO2/partially oxidized amorphous Si/HfO2.《APPLIED PHYSICS LETTERS》.2006,第89卷033122-1-3页. * |
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Effective date of registration: 20190715 Address after: 221000 Miaoshan Road Semiconductor Accelerator 7 of Xuzhou Economic and Technological Development Zone, Xuzhou City, Jiangsu Province Patentee after: Xuzhou Zhongke Li Shengxin Energy Technology Co.,Ltd. Address before: 100029 Beijing city Chaoyang District Beitucheng West Road No. 3 Patentee before: Institute of Microelectronics, Chinese Academy of Sciences |
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