CN105470129B - A method of eliminating oxygen Thermal donor influences minority diffusion length - Google Patents
A method of eliminating oxygen Thermal donor influences minority diffusion length Download PDFInfo
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- CN105470129B CN105470129B CN201510863269.7A CN201510863269A CN105470129B CN 105470129 B CN105470129 B CN 105470129B CN 201510863269 A CN201510863269 A CN 201510863269A CN 105470129 B CN105470129 B CN 105470129B
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000001301 oxygen Substances 0.000 title claims abstract description 58
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000009792 diffusion process Methods 0.000 title claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 53
- 239000010703 silicon Substances 0.000 claims abstract description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 238000012360 testing method Methods 0.000 claims abstract description 8
- 230000008030 elimination Effects 0.000 claims abstract description 6
- 238000003379 elimination reaction Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 235000012431 wafers Nutrition 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 3
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L22/00—Testing or measuring during manufacture or treatment; Reliability measurements, i.e. testing of parts without further processing to modify the parts as such; Structural arrangements therefor
- H01L22/10—Measuring as part of the manufacturing process
- H01L22/12—Measuring as part of the manufacturing process for structural parameters, e.g. thickness, line width, refractive index, temperature, warp, bond strength, defects, optical inspection, electrical measurement of structural dimensions, metallurgic measurement of diffusions
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a kind of methods that elimination oxygen Thermal donor influences minority diffusion length, by the way that the boat temperature that goes out of cassette is increased to the generation temperature of oxygen Thermal donor or more, and by being quickly cooled down the temperature range for making silicon chip be generated quickly through oxygen Thermal donor during going out boat, the generation for avoiding oxygen Thermal donor, to improve the confidence level of monocrystalline silicon sheet surface photovoltage body of laws iron test result after high annealing.The method of the present invention need not change hardware condition, and feasibility is strong, and repeatability is high.
Description
Technical field
The present invention relates to field of semiconductor manufacture, and oxygen Thermal donor can be eliminated to few sub (electronics) more particularly, to one kind
The method of the influence of diffusion length.
Background technology
With IC industrial expansions, increasingly higher demands are proposed to the quality of Si materials, minority carrier in Si monocrystalline
Son (few son) diffusion length and minority carrier life time are the important physical parameters of a characterization material property being concerned.Few son is influenced to expand
One of the principal element for dissipating length and minority carrier life time is metal contamination.Because metal impurities can be by thermal process from the table of silicon chip
Face diffuses into inside, becomes gap iron atom, is very effective complex centre, can greatly promote the compound of carrier, reduces
Silicon chip minority carrier life, and then influence the Performance And Reliability of device.In P-type silicon, gap iron atom at normal temperatures, by one section
The wriggling of time can form iron boron compound (FeB) with boron atom.But iron boron compound holds very much under illumination condition
It easily decomposes and is transformed into gap iron atom.The electron capture coefficient of FeB compounds is only the 1/12 of gap iron atom, i.e. trapped electron
Ability it is relatively low.
The major parameter for weighing silicon chip metal contamination degree has surface metal concentration and body concentration of iron.Currently, high-precision is surveyed
The main method for trying wafer bulk concentration of iron is surface photovoltage (SPV) method, it be it is a kind of it is nondestructive, can comprehensive scanning survey
The advanced measurement method of Si polished silicon wafer minority carrierdiffusion lengths.Its test philosophy is that the laser first with different wave length shines
Radiosilicon piece measures FeB to few sub (electronics) diffusion length before decomposition；Then white light silicon chip certain time is used, iron boron pair is made
It decomposes and generates iron ion and boron ion；FeB is finally measured to few son (electricity after decomposition with the laser irradiation silicon chip of different wave length again
Son) diffusion length.Iron boron in silicon chip can be calculated to the diffusion length for decomposing few sub (electronics) in forward and backward silicon chip using FeB
To quantity, and then extrapolate the content of unit volume inner body iron in silicon chip, calculation formula is as follows：
NFe(atoms/cm3)=1.05 × 1016(1/L2 after-1/L2 before)
Wherein, LafterThe diffusion length of few son, L after being shone for white lightbeforeIt is diffusion length of the white light according to preceding son less.
Can be seen that SPV methods from above-mentioned calculation formula is the body concentration of iron in indirectly testing silicon chip, so, it is every can
The factor for influencing few sub (electronics) diffusion length, can all influence the calculated value of body concentration of iron to the end.It should be pointed out that due to
Laser light incident depth is limited, it can only measure the body concentration of iron of near-surface region.
Oxygen is the impurity of most important unintentional incorporation in pulling of silicon single crystal, and concentration is generally 1017~1018cm-3, usually
In hypersaturated state.Oxygen impurities are to be introduced in growth course due to melting the effect of Si and silica crucible, and equation is such as
Under：
Si+SiO2=2SiO
Part SiO volatilizees from bath surface, and part SiO is then decomposed in molten silicon, and equation is as follows：
SiO=Si+O
The oxygen of decomposition enters in silicon melt, and crystal is entered during subsequent crystallisation by cooling, occupies the gap of lattice
Position, among the silicon-silicon bond along<111>Deviate axial position.Interstitial oxygen concentration itself is electroneutral impurity, and it is dense that let it be to the greatest extent
Degree is 1018The order of magnitude will not influence the electric property of silicon.But oxygen impurities can but cause in subsequent heat treatment process
The electroactive base such as Thermal donor (it is 350~600 DEG C to generate temperature range) and new promoted university (it is 650~800 DEG C to generate temperature range)
Group generates, and to change the electric property of silicon single crystal significantly, or even p-type silicon can be transformed into n-type silicon, will greatly influenced then
Device fabrication.Oxygen impurities can form oxygen precipitation at 650 DEG C or so, these oxygen precipitations may be used also at 950~1000 DEG C
To grow up, or even form fault.Although oxygen precipitation is typically electrically inactive, it can be miscellaneous with some metals with induced defects
Matter together, forms complex centre.
The main purpose of wafer high temperature thermal annealing is to eliminate the crystal grown-in defects (COP) on the nearly surface layer of silicon chip, makes monocrystalline silicon
Piece surfacing.Meanwhile annealing process can make the high concentration interstitial oxygen concentration on pulling of silicon single crystal piece surface layer carry out external diffusion, make nearly table
Layer forms the very low region of an oxygen content.In the temperature-fall period that annealing finishes, since nearly surface layer oxygen content is relatively low, it is unfavorable for
It the forming core of oxygen precipitation and grows up.Furthermore the segregation and the close phase of oxygen precipitation of the generation due to new promoted university and silicon intermediate gap oxygen atom
It closes, so silicon chip will not generate new promoted university substantially in temperature-fall period.
It is logical due to going out boat temperature but since the anneal act of oxygen Thermal donor is reversible, and during boat drops in cooling
600 degree of temperature below are often used, thus just has a large amount of oxygen Thermal donor before going out boat and generates.This will be seriously affected subsequently
Few sub (electronics) diffusion length when SPV is tested, to obtain true body iron when application surface photovoltage method is tested
Concentration.
Invention content
It is an object of the invention to overcome drawbacks described above of the existing technology, a kind of elimination oxygen Thermal donor is provided to few son
The method that diffusion length influences can avoid out the cooling before boat and drop the generation of oxygen Thermal donor during boat, eliminates oxygen Thermal donor
Influence to few sub (electronics) diffusion length, to obtain true body concentration of iron when application surface photovoltage method is tested.
To achieve the above object, technical scheme is as follows：
A method of eliminating oxygen Thermal donor influences minority diffusion length, including：By silicon chip be sent into process duct in into
When the processing of row high-temperature thermal annealing, first passes through heating and carry out main technique, then, temperature in process duct is down to the generation of oxygen Thermal donor
It more than temperature is used as out boat temperature to carry out out boat and drop boat, and silicon chip is persistently quickly cooled down during dropping boat, make silicon
The temperature range that piece generates during going out boat quickly through oxygen Thermal donor, oxygen is generated to avoid silicon chip again in cooling procedure
Thermal donor；And then the body concentration of iron using SPV method test silicon wafers.
Preferably, go out boat temperature and be not less than 600 degree.
Preferably, go out boat temperature and be not less than 610 degree.
Preferably, it is 610~700 degree to go out boat temperature.
Preferably, when carrying out high-temperature thermal annealing processing, protective gas is passed through into process duct.
Preferably, the protective gas includes that nitrogen, hydrogen, inert gas are at least one of.
Preferably, the shield gas flow rate is 5~40SLM.
Preferably, during dropping boat, it is passed through nitrogen using circulating fan, silicon chip is persistently quickly cooled down.
Preferably, drop boat rate is 100~300mm/min.
Preferably, during dropping boat, silicon chip is quickly cooled to 350 degree or less.
It can be seen from the above technical proposal that the present invention is by by the generation for going out boat temperature and being increased to oxygen Thermal donor of cassette
It more than temperature, and by being quickly cooled down the temperature range for making silicon chip be generated quickly through oxygen Thermal donor during going out boat, avoids
The generation of oxygen Thermal donor, to improve the credible of monocrystalline silicon sheet surface photovoltage body of laws iron test result after high annealing
Degree.The method of the present invention need not change hardware condition, and feasibility is strong, and repeatability is high.
Description of the drawings
Fig. 1 is the method flow that a kind of elimination oxygen Thermal donor of a preferred embodiment of the present invention influences minority diffusion length
Figure.
Specific implementation mode
Below in conjunction with the accompanying drawings, the specific implementation mode of the present invention is described in further detail.
In specific implementation mode of the invention below, referring to Fig. 1, Fig. 1 is one kind of a preferred embodiment of the present invention
Eliminate the method flow diagram that oxygen Thermal donor influences minority diffusion length.As shown in Figure 1, a kind of elimination oxygen Thermal donor of the present invention
The method that minority diffusion length is influenced, it may include following steps：
As shown in frame 01, the first step：In silicon chip transmission system, silicon chip is placed in cassette using manipulator, and leads to
It crosses bearing system cassette is sent into process duct, to carry out high-temperature thermal annealing processing.
The cassette can be used SiC or quartz material, and other materials suitable for high-temperature technology cassette.
As shown in frame 02, second step：It is passed through protective gas, and the temperature in process duct is risen into reaction and requires temperature, into
The main technique of row.
The protective gas may include at least one of in nitrogen, hydrogen, inert gas, such as can be passed through high-purity argon
The mixed gas of gas or argon gas and hydrogen；The flow that is passed through of the protective gas can be 5~40SLM.It can be by the temperature in process duct
It can be 30~60 minutes that degree, which rises to reaction from 600~650 DEG C and requires 1100~1250 DEG C of temperature, reaction time,.
As shown in frame 03, third step：Temperature in process duct is reduced to the generation temperature of oxygen Thermal donor or more to be used as out
Boat temperature, and carry out out boat and drop boat.
In protective gas atmosphere, the temperature in process duct can be reduced to and be used as boat temperature not less than 600 degree, and is steady
Determine certain time.It can prevent silicon chip in dropping to the temperature stabilization process before can going out in boat temperature course and going out boat in this way, silicon
The generation again of oxygen Thermal donor in piece.
The temperature-fall period of existing high annealing typically from the high temperature at a temperature of reaction requirement is slowly decreased to that boat temperature can be gone out
Degree, and stablize 10min or so boat temperature spot can be gone out, then boat drops.It is to use 600 degree of temperature below that it, which can go out boat temperature, because
This, a large amount of oxygen Thermal donor (it is 350~600 DEG C to generate temperature range) is just had before going out boat and is generated.
Based on this, the present invention has carried out specific aim improvement, and the temperature for going out boat is increased to 600 degree or more, thus can be with
It is effectively prevented from the generation again of oxygen Thermal donor.
As a preferred embodiment, can be not less than by going out boat temperature by 610 degree；It is possible to further which boat temperature control will be gone out
System is between 610~700 degree.
As shown in frame 04, the 4th step：During dropping boat, silicon chip is persistently quickly cooled down.
Under silicon chip transmission system, cassette can be removed into process duct with appropriate speed by motor；Meanwhile it is micro- to open equipment
The silicon chip cooling device of environment, such as circulating fan, and it is passed through nitrogen, make silicon chip under the action of flowing gas, quickly takes away
When dropping boat and silicon chip and cassette are taken out of out of boiler tube after drop boat heat, accelerates the cooling rate of silicon chip, can also realize and keep away
Exempt from the generation again of oxygen Thermal donor.
As an optional embodiment, drop boat rate can be 100~300mm/min, preferably 200mm/min, and incite somebody to action
Silicon chip is quickly cooled to 350 degree hereinafter, making the temperature range that silicon chip generates during going out boat quickly through oxygen Thermal donor.
Finally, as shown in frame 05, the 5th step：After being fully cooled, silicon chip is taken out from cassette by manipulator, it is then sharp
With the body concentration of iron of SPV method test silicon wafers, you can obtain true body concentration of iron.
In conclusion the present invention is by the boat temperature that goes out of cassette by being increased to the generation temperature of oxygen Thermal donor or more, and lead to
The temperature range for being quickly cooled down and silicon chip being made to be generated quickly through oxygen Thermal donor during going out boat is crossed, the production of oxygen Thermal donor is avoided
It is raw, to improve the confidence level of monocrystalline silicon sheet surface photovoltage body of laws iron test result after high annealing.The method of the present invention
Hardware condition need not be changed, feasibility is strong, and repeatability is high.
Above-described to be merely a preferred embodiment of the present invention, the embodiment is not to be protected to limit the patent of the present invention
Range, therefore equivalent structure variation made by every specification and accompanying drawing content with the present invention are protected, similarly should be included in
In protection scope of the present invention.
Claims (10)
1. a kind of method eliminated oxygen Thermal donor and influenced on minority diffusion length, which is characterized in that including：Silicon chip is being sent into work
When carrying out high-temperature thermal annealing processing in skill pipe, first passes through heating and carry out main technique, then, temperature in process duct is down to oxygen heat and is applied
It more than main generation temperature is used as out boat temperature to carry out out boat and drop boat, and fast quickly cooling is persistently carried out to silicon chip during dropping boat
But, the temperature range for making silicon chip be generated quickly through oxygen Thermal donor during going out boat, in cooling procedure again to avoid silicon chip
Secondary generation oxygen Thermal donor；And then the body concentration of iron using SPV method test silicon wafers.
2. the method according to claim 1 eliminated oxygen Thermal donor and influenced on minority diffusion length, which is characterized in that go out boat
Temperature is not less than 600 degree.
3. the method according to claim 2 eliminated oxygen Thermal donor and influenced on minority diffusion length, which is characterized in that go out boat
Temperature is not less than 610 degree.
4. the method according to claim 3 eliminated oxygen Thermal donor and influenced on minority diffusion length, which is characterized in that go out boat
Temperature is 610~700 degree.
5. the method according to claim 1 eliminated oxygen Thermal donor and influenced on minority diffusion length, which is characterized in that carry out
When high-temperature thermal annealing processing, protective gas is passed through into process duct.
6. the method according to claim 5 eliminated oxygen Thermal donor and influenced on minority diffusion length, which is characterized in that described
Protective gas includes that nitrogen, hydrogen, inert gas are at least one of.
7. the method according to claim 5 or 6 eliminated oxygen Thermal donor and influenced on minority diffusion length, which is characterized in that
The shield gas flow rate is 5~40SLM.
8. the method according to claim 1 eliminated oxygen Thermal donor and influenced on minority diffusion length, which is characterized in that dropping
During boat, it is passed through nitrogen using circulating fan, silicon chip is persistently quickly cooled down.
9. the method that the elimination oxygen Thermal donor according to claim 1 or 8 influences minority diffusion length, which is characterized in that
Drop boat rate is 100~300mm/min.
10. the method that the elimination oxygen Thermal donor according to claim 1 or 8 influences minority diffusion length, which is characterized in that
Silicon chip is quickly cooled to 350 degree or less.
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| CN113721076A (en) * | 2021-08-09 | 2021-11-30 | 上海新昇半导体科技有限公司 | Method for measuring resistivity of silicon wafer |
| CN115369486B (en) * | 2022-10-26 | 2023-04-11 | 新美光(苏州)半导体科技有限公司 | Method for solving problem of false height of resistance and inversion of conductivity type of abnormal silicon rod |
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| JP2005223293A (en) * | 2004-02-09 | 2005-08-18 | Sumitomo Mitsubishi Silicon Corp | Annealing method of silicon wafer, and the silicon wafer |
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|---|---|---|---|---|
| CN1319253A (en) * | 1998-09-02 | 2001-10-24 | Memc电子材料有限公司 | Non-oxygen precipitating czochralski silicon wafers |
| CN1796621A (en) * | 2001-06-28 | 2006-07-05 | 三星电子株式会社 | Rapid thermal annealing for silicon wafers and silicon wafers fabricated thereby |
| JP2004207601A (en) * | 2002-12-26 | 2004-07-22 | Sumitomo Mitsubishi Silicon Corp | Method for heat treatment of silicon wafer |
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