CN102683476A - Oxygenic n-type beta-ferrosilicon (FeSi2) and manufacturing method thereof - Google Patents
Oxygenic n-type beta-ferrosilicon (FeSi2) and manufacturing method thereof Download PDFInfo
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- CN102683476A CN102683476A CN2011100692367A CN201110069236A CN102683476A CN 102683476 A CN102683476 A CN 102683476A CN 2011100692367 A CN2011100692367 A CN 2011100692367A CN 201110069236 A CN201110069236 A CN 201110069236A CN 102683476 A CN102683476 A CN 102683476A
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Abstract
Oxygenic n-type beta-ferrosilicon (FeSi2) nano-wire is synthesized by chemical vapor deposition (CVD). Within the temperature range from 650 DEG C to 950 DEG C, the structure of the n-type beta-phase FeSi2 generated by carrying the predecessor FeCl3 to react on a silicon base plate by a carrier gas is confirmed by analysis and mutual comparison of XRD (x-ray diffraction) and TEM (transverse electric and magnetic field), and the structural appearance is directly viewed by the TEM. On the basis of the above analysis, a steady method for synthesizing n-type beta-ferrosilicon (FeSi2) nano-wire is found within the temperature range from 650 DEG C to 950 DEG C.
Description
Technical field
The present invention is about a kind of iron suicide (FeSi
2) manufacturing approach, particularly a kind of oxygen containing n-type beta-iron silicide (FeSi
2) manufacturing approach.
Background technology
FeSi
2Coming to light at present can be with four kinds of different existing mutually, and first crystalline phase is α-FeSi
2,, have the character of metal at high temperature more stable (＞940 ℃); Second crystalline phase is β-FeSi
2,, be a kind of semi-conducting material at low temperature more stable (＜940 ℃); In recent years, many research teams found can grow on the Si (111) the thin FeSi of one deck separately
2, can divide into two kinds haply at present.Be respectively γ-FeSi
2And s-FeSi
2These can't be found on general phasor mutually, because these structures can not form three-dimensional bulk, but form that can film exists.
β-FeSi
2Have semi-conductive character, and more stable when temperature is lower than 940 ℃, have the direct gap of an about 0.87eV.One has the compound semiconductor of d orbital electronics at outermost layer, and light is had a higher absorption coefficient; And β-FeSi
2In contain the Fe atom, so also have the electronics of d orbital, and higher absorption coefficient is arranged, its conversion efficiency is about 23% on the Theoretical Calculation, and has high absorption coefficient (1*105cm-1) via experiment confirm.Because light is had high absorptivity, can do thinlyyer so make assembly, not only material can be saved but also the cost of processing procedure can be reduced; These character make β-FeSi
2Be fit to bring conduct solar cell material and infrared detector cheaply.
2005, people such as Lian Ouyang successfully utilized gas phase to synthesize the nano wire of FeSi, and they propose its reaction mechanism and have following two kinds:
FeCl
2(s)+Cl
2(g)+2Si (s)-→ FeSi (s)+SiCl
4(g) reach
2Fe
2Cl
6(g)+7Si(s)—→4FeSi(s)+3SiCl
4(g)
Yet the phasor that can know Fe-Si from phasor is very complicated in fact, even it is proportional to have identical element set, also might grow the different crystalline lattice phase, and different meeting has distinct character.
Therefore have a kind of needs, hope can find one group of stable parameter can effectively control the growth of Fe-Si, whether various conditions can influence it and form, and obtain required n-type beta-iron silicide (FeSi the influence of Fe-Si nano wire
2) nano wire.
The present invention promptly to this demand, proposes a kind of n-type beta-iron silicide (FeSi
2) manufacturing approach.
Summary of the invention
The object of the present invention is to provide a kind of beta-iron silicide (FeSi
2) manufacturing approach, with chemical vapour deposition technique need not high vacuum and oxygen containing n-type β-FeSi
2
For reaching above-mentioned purpose and other purpose, first viewpoint of the present invention is instructed a kind of n-type beta-iron silicide (FeSi
2) manufacturing approach, towards being on the Silicon Wafer of (100) or (111) with the oxygen containing n-type of chemical vapour deposition (CVD) β-FeSi
2, comprise the following step: with one three district's Quartz stove tube, the predecessor FeCl that first district's placing response is required
3, second and third district then puts into cleans Silicon Wafer later, and the pressure in the Quartz stove tube is evacuated to 7.0 * 10
-2Feed nitrogen (N behind the torr
2) to 10torr, again pressure is extracted into 7.0 * 10
-2Torr, this action is repeatedly for several times; Be warmed up to 140 ℃, hold temperature and the crystallization water removed in one hour; Feed required current-carrying gas, current-carrying gas is 80-99% argon (Ar) and 1-20% hydrogen (H
2), be preferably 80%Ar and 20%H
2, or be entirely nitrogen (N
2), flow slowly takes predecessor on the silicon substrate of question response greater than 15sccm, oxygen is then from the oxide layer on the Silicon Wafer (native oxide), make metal chloride with the preceding elder generation and the oxygen reaction of silicon substrate reaction, and produce Fe-O; The temperature in second district and the 3rd district is raised to reaction temperature and keeps a period of time, and this reaction temperature is 650 ℃ to 950 ℃; Stop heating, but current-carrying gas continues still predecessor is transported on the silicon substrate, also at leisure heat taken away simultaneously, slowly anneal and oxygen containing n-type β-FeSi
2
Description of drawings
Fig. 1 is the chemical vapour deposition (CVD) three district's boiler tube profiles according to the embodiment of the invention.
Fig. 2 is with N according to the embodiment of the invention
2For current-carrying gas is descended oxygen containing n-type β-FeSi for 900 ℃ in reaction temperature
2XRD diffraction signal.
Fig. 3 is with 80%Ar and 20%H according to the embodiment of the invention
2For current-carrying gas is descended oxygen containing n-type β-FeSi for 900 ℃ in reaction temperature
2XRD diffraction signal.
Fig. 4 is with 80%Ar and 20%H according to the embodiment of the invention
2For current-carrying gas is descended oxygen containing n-type β-FeSi for 900 ℃ in reaction temperature
2The SEM image.
Fig. 5 A, 5B are according to the β-FeSi that has the O atom around the Si of embodiment of the invention center
2Structural representation and its theoretical XRD.
Fig. 6 is according to embodiment of the invention β-FeSi
2The EDS of TEM analyze.
Fig. 7 is according to embodiment of the invention β-FeSi
2The diffraction point of TEM.
Fig. 8 is about 100nm according to embodiment of the invention width, and length is about β-FeSi of 2 microns
2The resistance view that nano wire measures under different temperatures.
The primary clustering symbol description
101 3 district's Quartz stove tubes, 102 predecessor FeCl3
103 Silicon Wafers, 104 Silicon Wafers
105 heaters, 106 current-carrying gas
107 mechanical pumps
Embodiment
Reach the easier understanding fully of other purpose and advantage more than of the present invention with reference to the explanation of following reference diagram and most preferred embodiment.
Please refer to Fig. 1, Fig. 1 is the chemical vapour deposition (CVD) three district's boiler tube profiles according to the embodiment of the invention.Three district's Quartz stove tubes, 101 having heaters 105, current-carrying gas 106 flows into from an end, and current-carrying gas is 80-99% argon (Ar) and 1-20% hydrogen (H
2), be preferably 80%Ar and 20%H
2, also can be fully with nitrogen (N
2), the predecessor FeCl that first district's placing response is required
3102, second and third district then puts into cleans Silicon Wafer 103,104 later, Silicon Wafer towards being (100), (110) or (111); Pressure in the Quartz stove tube 101 is evacuated to 7.0 * 10 with mechanical pump 107
-2Feed nitrogen (N behind the torr
2) to 10torr, again pressure is extracted into 7.0 * 10
-2Torr, this action is repeatedly for several times; Be warmed up to 140 ℃ then, hold temperature and the crystallization water removed in one hour; Feed required current-carrying gas; The flow of current-carrying gas is greater than 15sccm; On the silicon substrate 103,104 that predecessor 102 is slowly taken to question response, oxygen makes metal chloride react elder generation and oxygen reaction before with silicon substrate then from the oxide layer on the Silicon Wafer (native oxide); And produce Fe-O, form FeSi with the substrate reaction again
2The temperature in second district and the 3rd district is raised to reaction temperature and keeps a period of time, and reaction temperature is 650 ℃ to 950 ℃; Deposition finishes and stops heating, but current-carrying gas still continues predecessor is transported on the silicon substrate, also at leisure heat is taken away simultaneously, slowly anneal and oxygen containing n-type β-FeSi
2
Please refer to Fig. 2, Fig. 2 is with N according to the embodiment of the invention
2For current-carrying gas is descended oxygen containing n-type β-FeSi for 900 ℃ in reaction temperature
2XRD diffraction signal.Show among the figure except { 220} has the stronger diffraction signal, and all the other diffraction peaks then appear between 45～50 degree, have good crystallinity.Please refer to Fig. 3, Fig. 3 is with 80%Ar and 20%H according to the embodiment of the invention
2For current-carrying gas is descended oxygen containing n-type β-FeSi for 900 ℃ in reaction temperature
2XRD diffraction signal.For fear of product too much oxide appears, with 80%Ar and 20%H
2Replace N
2Be current-carrying gas, oxygen containing n-type β-FeSi
2XRD diffraction signal stronger.
Please refer to Fig. 4, Fig. 4 is with 80%Ar and 20%H according to the embodiment of the invention
2For current-carrying gas is descended oxygen containing n-type β-FeSi for 900 ℃ in reaction temperature
2The SEM image.Can see that surface aggregation becomes the block structure of a grain, has explained β-FeSi among the XRD just
2Crystallization, and have size thread different in size around the block structure.
Table 1 shows 900 ℃, 2 hours, and 80%Ar+20%H
2, the resulting atom of 50sccm is formed, and can see that the O atom content has accounted for 1/3rd.
Table 1
Please refer to Fig. 5, Fig. 5 is according to the β-FeSi that has the O atom around the Si of embodiment of the invention center
2Structural representation and its theoretical XRD.Utilize Carine software to draw after the structure, the signal of its XRD of emulation again is at β-FeSi
2Middle adding O atom, and all O atoms all are positioned at the centre of the Si atom and the Fe atom at lattice center.
Please refer to Fig. 6, Fig. 6 is according to embodiment of the invention β-FeSi
2The EDS of TEM analyze.Can confirm to contain Fe, Si, O atom in the composition of nano wire.
Please refer to Fig. 7, Fig. 7 is according to embodiment of the invention β-FeSi
2The diffraction point of TEM.The growth direction that can judge nano wire is a court<004>Direction is grown up, and is consistent with XRD diffraction peak before, β-FeSi when nano wire forms
2Can have significantly<004>The diffraction signal.
Please refer to Fig. 8, Fig. 8 is about 100nm according to embodiment of the invention width, and length is about β-FeSi of 2 microns
2The resistance view that nano wire measures under different temperatures.Can find that resistance descends along with the rising of temperature, this is the characteristic that typical semiconductive material just has.The resistance value of (temperature is 2K) is 1677934 nurses difficult to understand under the liquid helium atmosphere, and along with temperature rises and resistance decline, this is because the electric charge carrier in the material forms the line activated state because temperature raises.Can be when low temperature be generally considered to be and contribute by less atom with regard to d/d electric charge carrier.Therefore, we think that oxygen atom contained in the material contributed conductivity.And about 77K, the resistance downward trend eases up, and is commonly considered as because the lattice vibrations in the material have increased part resistance on the contrary, and made the overall electrical resistance downward trend ease up.
By the detailed description of above preferable specific embodiment, be to hope know more to describe characteristic of the present invention, and be not to come category of the present invention is limited with the above-mentioned preferred embodiments that is disclosed with spiritual.Opposite, its objective is that hope can contain in the patent category of being arranged in of various changes and tool equality institute of the present invention desire application.
Claims (9)
1. n-type beta-iron silicide (FeSi
2) manufacturing approach, on Silicon Wafer with the oxygen containing n-type of chemical vapour deposition (CVD) β-FeSi
2, comprise the following step at least:
With a multi-region Quartz stove tube, the required predecessor of first district's placing response, second and third district then puts into cleans Silicon Wafer later, and the pressure in the Quartz stove tube is evacuated to 1 to 10
-3Feed inert gas 1 behind the torr to 30torr, again pressure is extracted into 1 to 10
-3Torr, this action is repeatedly for several times;
Be warmed up to more than the boiling point of water, hold temperature and the crystallization water removed in one hour;
Feed required current-carrying gas; The flow of this current-carrying gas is greater than 15sccm; Predecessor is slowly taken on the silicon substrate of question response, oxygen makes metal chloride react elder generation and oxygen reaction before with silicon substrate then from the oxide layer on the Silicon Wafer (native oxide); And produce Fe-O, form FeSi with the substrate reaction again
2
The temperature in second district and the 3rd district is raised to reaction temperature and keeps a period of time, and this reaction temperature is 650 ℃ to 950 ℃;
Stops heating, under vacuum, rise again, but current-carrying gas still continues predecessor is transported on the silicon substrate, also at leisure heat is taken away simultaneously to room temperature, slowly anneal and oxygen containing n-type β-FeSi
2
2. manufacturing approach as claimed in claim 1 is characterized in that: this predecessor is the halide of iron.
3. manufacturing approach as claimed in claim 1 is characterized in that: this predecessor is ferrous halide.
4. manufacturing approach as claimed in claim 1 is characterized in that: this inert gas is nitrogen (N
2).
5. manufacturing approach as claimed in claim 1 is characterized in that: this Silicon Wafer towards for (100).
6. manufacturing approach as claimed in claim 1 is characterized in that: this Silicon Wafer towards for (111).
7. manufacturing approach as claimed in claim 1 is characterized in that: this Silicon Wafer towards for (110).
8. manufacturing approach as claimed in claim 1 is characterized in that: this current-carrying gas is 80-99% argon (Ar) and 1-40% hydrogen (H
2), be preferably 80% argon (Ar) and 20% hydrogen (H
2).
9. manufacturing approach as claimed in claim 1 is characterized in that: this current-carrying gas is nitrogen (N
2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100692367A CN102683476A (en) | 2011-03-18 | 2011-03-18 | Oxygenic n-type beta-ferrosilicon (FeSi2) and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100692367A CN102683476A (en) | 2011-03-18 | 2011-03-18 | Oxygenic n-type beta-ferrosilicon (FeSi2) and manufacturing method thereof |
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|---|---|
| CN102683476A true CN102683476A (en) | 2012-09-19 |
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|---|---|---|---|
| CN2011100692367A Pending CN102683476A (en) | 2011-03-18 | 2011-03-18 | Oxygenic n-type beta-ferrosilicon (FeSi2) and manufacturing method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200600619A (en) * | 2004-06-30 | 2006-01-01 | Univ Nat Tsing Hua | Single crystal metallic silicide-nanowire and method producing the same |
| US20100164110A1 (en) * | 2006-08-17 | 2010-07-01 | Song Jin | Metal silicide nanowires and methods for their production |
-
2011
- 2011-03-18 CN CN2011100692367A patent/CN102683476A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200600619A (en) * | 2004-06-30 | 2006-01-01 | Univ Nat Tsing Hua | Single crystal metallic silicide-nanowire and method producing the same |
| US20100164110A1 (en) * | 2006-08-17 | 2010-07-01 | Song Jin | Metal silicide nanowires and methods for their production |
Non-Patent Citations (1)
| Title |
|---|
| J.L.REGOLINI.ETAL: "Selective and Epitaxial Deposition of β-FeSi2 onto Silicon by RTP-CVD", 《J. PHYS. Ⅲ FRANCE 2》, 31 August 1992 (1992-08-31) * |
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Application publication date: 20120919 |