CN102181919B - Method for controlling resistivity of head of Czochralski silicon - Google Patents

Method for controlling resistivity of head of Czochralski silicon Download PDF

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CN102181919B
CN102181919B CN 201110092541 CN201110092541A CN102181919B CN 102181919 B CN102181919 B CN 102181919B CN 201110092541 CN201110092541 CN 201110092541 CN 201110092541 A CN201110092541 A CN 201110092541A CN 102181919 B CN102181919 B CN 102181919B
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resistivity
silicon
crystal
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test
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CN102181919A (en
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李建弘
张雪囡
李翔
沈浩平
董兆清
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Central leading semiconductor materials Co., Ltd
Inner Mongolia Central Leading Semiconductor Materials Co.,Ltd.
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Tianjin Huanou Semiconductor Material Technology Co Ltd
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Abstract

The invention discloses a method for controlling resistivity of a head of Czochralski silicon. The method mainly comprises the following steps of: 1, preparing a test monocrystal; 2, processing the test monocrystal into a test sample, and testing the resistivity of the test sample; 3, if the resistivity of the test sample does not meet the requirements, working out the mass of doped alloy, and performing secondary doping; and 4, preparing a test monocrystal again, testing the resistivity of the test sample, and if the resistivity of the test sample still does not meet the requirements, performing third or fourth doping until the resistivity meets the requirements. The method has the advantages that: the resistivity of the finished product of monocrystal can be accurately controlled, the deviation between the resistivity of the finished product of silicon monocrystal and the target resistivity is controlled in a range of 1 to 3 ohm.cm, the yield of the finished product of silicon monocrystal is improved by 8 percent, and the cost is lowered by about 20 percent.

Description

A kind of method of controlling the czochralski silicon monocrystal head resistivity
Technical field
The present invention relates to the working method of silicon single-crystal, particularly a kind of method of controlling the czochralski silicon monocrystal head resistivity.
Background technology
The traditional method of control single crystal silicon resistivity is that this process of preparation of raw material is controlled; And then according to parameters such as silicon single-crystal target resistivity, single heat charging capacity, polycrystal raw material resistivity, resistance alloys rate, preparation technologies; Calculate the proportional quantity (mixing first) of polycrystal raw material and alloy; Carrying out raw material shove charge, heat fused, crystal-pulling then, is control method before a kind of typical shove charge.But prepare in the process at silicon single-crystal subsequently; Can't accurately control single crystal silicon resistivity; And influenced by raw material, resistance alloys rate test accuracy and operation deviation etc.; Often make finished product single crystal silicon resistivity and silicon single-crystal target resistivity serious deviation (8~15 Ω .cm) occur, cause the finished product single crystal silicon resistivity not reach target call, qualification rate is low, cost is high.
Summary of the invention
In order to address the above problem, the resistivity after the shove charge of further accurate control silicon single-crystal, the present invention researches and develops a kind of method of controlling the czochralski silicon monocrystal head resistivity.This method is that resistivity measurement carries out secondary or repeatedly adulterated method per sample in preparation silicon single-crystal sample process.Can know that according to existing diffusion and solidification theory doping agent is certain rules and is distributed in the whole silicon crystal bar, under the constant situation of preparation technology; Dopant distribution can not become yet, and the size of the big or small direct reaction resistivity of concentration of dopant, this that is to say; Silicon single-crystal each several part resistivity distribution is corresponding one by one with the distribution of doping agent; Also be identical rule and distribute, therefore, if the resistivity (head resistivity) of the preliminary growth phase of known silicon single-crystal; Just can extrapolate bulk silicon monocrystalline resistivity distribution, thereby reach the purpose of control silicon single-crystal overall resistivity according to this resistivity.
The present invention after the silicon raw material melts fully, at first prepares the specimen of small dia, short length monocrystalline according to above-mentioned analytical results; And it is carried out resistivity measurement; Thereby obtain the head resistivity of silicon single-crystal, calculate the doped alloys quality, carry out secondary subsequently or the operation of repeatedly mixing with this head resistivity; Reach the purpose of accurate control silicon single-crystal head resistivity, and then form control fully the silicon single-crystal overall resistivity.
The technical scheme that the present invention taked is: a kind of method of controlling the czochralski silicon monocrystal head resistivity is characterized in that comprising the steps:
Step 1. raw material carries out the drawing of test silicon monocrystalline after all melting and finishing;
Step 2. after the test silicon crystal-pulling finishes, take out the test silicon monocrystalline, test silicon single-wafer cylinder partial is processed into the plane, obtain specimen;
Step 3. afterwards, the planar section of specimen is carried out resistivity measurement with the four point probe resistivity tester, and record resistivity measurement value;
Step 4. the resistivity measurement value of compare test sample and silicon single-crystal target resistivity value; Calculate the resistivity measurement value of specimen and the difference of silicon single-crystal target resistivity; If the resistivity measurement value of specimen is than silicon single-crystal target resistivity value >=5 Ω .cm; Then carry out the operation of following steps, otherwise the resistivity measurement value of specimen satisfies the requirement of silicon single-crystal target resistivity, directly carries out normal pulling operation;
Step 5. according to the resistivity measurement value of specimen and the difference of silicon single-crystal target resistivity value, calculate required doped alloys quality;
Step 6. the doped alloys that will calculate certain mass mixes in the silicon melt;
Step 7. after the complete melt-blended of doped alloys is even, repeats step 1 to step 3, and calculate the resistivity measurement value of specimen and the difference of silicon single-crystal target resistivity value once more;
Step 8. if the resistivity measurement value of calculating the gained specimen for the second time is than silicon single-crystal target resistivity value >=5 Ω .cm; Then repeat step 5 to step 7; Until the resistivity measurement value of specimen than silicon single-crystal target resistivity value<5 Ω .cm; Then stop to mix, the resistivity of specimen satisfies the requirement of silicon single-crystal target resistivity, promptly accomplishes the control of silicon single-crystal head resistivity.
The invention has the beneficial effects as follows: through implementing this method, can accurately control the finished product single crystal silicon resistivity, make finished product single crystal silicon resistivity and target resistivity deviation control in 1-3 Ω .cm scope, finished silicon monocrystalline qualification rate improves 8%, and cost reduces about 20%.
Description of drawings
Fig. 1 is a test silicon monocrystalline synoptic diagram of the present invention.
Embodiment
Below in conjunction with specific embodiment, further specify the present invention and how to realize.
Embodiment 1: it is Kayex CG6000 vertical pulling stove that silicon single-crystal prepares equipment used, 16 cun thermal fields, 35 kilograms of charging capacitys.Its concrete steps are following:
1. preparation of raw material: preparation polycrystalline silicon raw material M Polycrystalline=35kg, and calculate institute's doped alloys (alloy of doping agent and silicon) mass M according to original resistivity of polycrystalline silicon raw material and prepared silicon single-crystal target resistivity AlloyPolycrystalline silicon raw material base phosphorus resistivity is ρ among this embodiment Polycrystalline=1000 Ω .cm, the target resistivity ρ of finished silicon monocrystalline Target=50 Ω .cm, doping agent alloy (P-Si) electricalresistivity Alloy=0.04 Ω .cm can calculate phosphorus element content ω in the above-mentioned polycrystalline silicon raw material according to being numbered GB/T 13389-92 " phosphorus single crystal silicon resistivity and concentration of dopant conversion rules are mixed in boron-doping " national standard Polycrystalline=4.2 * 10 12Atoms/cm 3, target resistivity is phosphorus element content ω in the silicon single-crystal of 50 Ω .cm Target=8.64 * 10 13Atoms/cm 3, doping agent alloy phosphorus element content ω Alloy=3.53 * 10 17Atoms/cm 3Therefore, required doping agent alloy mass can be obtained by following formula (1):
(M Polycrystalline+ M Alloy) * ω Target-M Polycrystalline* ω Polycrystalline=M Alloy* ω Alloy-----------(1)
Because doping agent alloy mass M AlloyVery little, with respect to the polycrystal raw material mass M PolycrystallineCan ignore, therefore final gained silicon single-crystal quality can be reduced to polycrystal raw material quality (M Monocrystalline=M Polycrystalline+ M Alloy≈ M Polycrystalline), with above-mentioned numerical value substitution (1) formula, calculate and should add doping agent alloy mass M in the present embodiment blending process Alloy=8.17g (promptly doped alloys quality) first.
2. the raw material for preparing is put in the Kayex CG6000 type vertical pulling stove; The heatingization material; After the change material finishes, heating power is adjusted to seeding power (this embodiment seeding power is 55kw), set seeding temperature spot (this embodiment seeding temperature spot is 1450 SP); Under this temperature, stable silicon liquation 10 minutes.
3. the drawing of test silicon monocrystalline: seed crystal reduced to silicon liquid level contact, the manual setting pulling rate carries out the seeding operation; For discharging dislocation fully; Should make the thin neck length degree of seeding be not less than 1.2 times of test silicon single crystal diameter, the thin neck length degree of seeding is 4cm among this embodiment, and the thin neck diameter of seeding is 3.5mm; Carry out shouldering after seeding finishes and take on operation with changeing, shouldering speed should be tried one's best slowly, avoids too fast and the generation dislocation, also is simultaneously that the handled easily of back commentaries on classics shoulder is got ready; When shoulder diameter acquires a certain degree; Will change the shoulder operation in advance, guarantee that the diameter after commentaries on classics is takeed on reaches the requirement of isometrical diameter, isometrical diameter should be controlled between the 2cm-3cm; Should be less than 2cm; Otherwise because diameter is too little, putting changes shoulder excessive velocities (thermal field decision), causes because of the actually operating difficulty dislocation luxuriant phenomenon of breaking to occur; Isometrical diameter should not surpass 3cm yet simultaneously, otherwise causes the waste in too much raw material and man-hour, finally causes cost to rise.The isometrical diameter of test silicon monocrystalline is 2.8cm (optimum diameter is 3cm) in the present embodiment; Change the shoulder back and get into isometrical maintenance process, electrical path length such as maintenance are answered >=4cm, can be processed into specimen smoothly to guarantee the test silicon monocrystalline, and the medium electrical path length of present embodiment is 4.2cm; The operation that finishes up at last, epilog should slowly be carried out, and the control pulling rate makes afterbody become taper, and it is pointed that tail end becomes, and then avoid producing dislocation and cause the failure of test silicon crystal-pulling.
4. the processing of specimen: the test silicon monocrystalline is taken out, after cooling finishes, the surface is processed with oilstone; Choose the arc surface (the preferably part between rib and the rib) of test silicon monocrystalline equal-diameter part, it is ground into the plane, the planar size is advisable to be fit to the test of four point probe resistivity tester; Be generally 5mm * 5mm size,, grind next test plane then with test silicon monocrystalline rotation proper angle; So grind plane 2-3 of test,, grind 3 on plane in the present embodiment altogether so that more number of test points certificate to be provided; Grind and to exert oneself in the planarization process evenly as far as possible, grind direction and carry out, avoid intersecting in opposite directions grinding along a direction; Reduce to grind affected layer, to increase the accuracy of resistivity measurement as far as possible.
5. adopt SDY-4 four point probe tester that the specimen of completion of processing is carried out resistivity measurement; The test position is the plane of above-mentioned processing; Each plane test three times; Get the MV and the record of three test datas, it is following to survey three planar average resistivity data in the present embodiment: 62.1 Ω .cm, 63.6 Ω .cm, 62.7 Ω .cm, get the resistivity value of the MV 62.8 Ω .cm of above-mentioned three data as specimen again.
6. can know by above test that the resistivity value 62.8 Ω .cm of specimen are worth the big 12.8 Ω .cm (difference) of 50 Ω .cm than the target resistivity of silicon single-crystal, do not reach the product parameters requirement, need carry out the second time and mix.The content of phosphoric equates with the content of phosphoric in the existing silicon melt in the known prepared specimen; Therefore can draw the content of phosphoric in the silicon melt by the resistivity value of specimen; Same according to the method in the preparation raw material step, according to being numbered the content ω that GB/T 13389-92 " phosphorus single crystal silicon resistivity and concentration of dopant conversion rules are mixed in boron-doping " national standard can calculate phosphoric in silicon melt this moment Melt=6.83 * 10 13Atoms/cm 3, secondly can know phosphorus element content ω in institute's doped alloys Alloy=3.53 * 10 17Atoms/cm 3, phosphorus element content ω in the target melt Target=8.64 * 10 13Atoms/cm 3, melt quality can approximate batching quality, i.e. M Melt≈ M Polycrystalline+ M AlloySo=35kg is by following formula: (M Polycrystalline+ M Alloy) * ω Target– M Melt* ω Melt=M Secondary alloy* ω AlloyCalculating can obtain: M Secondary alloy=1.79g.
7. adjustment silicon liquid temp carries out the silicon bowl and draws, after the preparation of silicon bowl finishes; Close plate valve in the stove,, open fire door last furnace chamber inflation; Load weighted doped alloys 1.79g is put in the silicon bowl, closes fire door and carry out replacement operator, after displacement finishes; The silicon bowl that carries doped alloys is immersed in the silicon liquid, accomplish for the second time and mix.
8. after secondary doping finishes, carry out steady temperature operation once more, set seeding temperature spot (this embodiment seeding temperature spot is 1450 SP), under this temperature, stable silicon liquid temp 10 minutes.
9. afterwards; Carry out the drawing of test silicon monocrystalline, the processing of specimen, the resistivity measurement of specimen once more according to above-mentioned the 1st~5 step; The resistivity value that finally obtains the specimen behind the secondary doping is 51.8 Ω .cm; Be worth the big 1.8 Ω .cm (difference) of 50 Ω .cm than silicon single-crystal target resistivity, phase difference<5 Ω .cm satisfies the requirement of silicon single-crystal target resistivity.
10. according to the 51.8 Ω .cm of the specimen resistivity value behind the above secondary doping, can know that the P constituent content is 8.3 * 10 in melt this moment 13Atoms/cm 3, and can judge that thus the melt after the doping satisfies the requirement that draws the finished product single crystal silicon resistivity, so operation afterwards can be prepared the finished silicon monocrystalline that resistivity meets the demands according to the czochralski silicon monocrystal preparation technology of routine.
Embodiment 2: it is Kayex CG6000 vertical pulling stove that silicon single-crystal prepares equipment used, 18 cun thermal fields, 55 kilograms of charging capacitys.Its concrete steps are following:
1. preparation of raw material: preparation polycrystalline silicon raw material M Polycrystalline=55kg, its basic phosphorus resistivity is ρ Polycrystalline=1200 Ω .cm, the target resistivity ρ of expection finished silicon monocrystalline Target=28 Ω .cm, doping agent alloy (P-Si) electricalresistivity Alloy=0.04 Ω .cm can calculate phosphorus element content ω in the above-mentioned polysilicon according to being numbered GB/T 13389-92 " phosphorus single crystal silicon resistivity and concentration of dopant conversion rules are mixed in boron-doping " national standard Polycrystalline=3.5 * 10 12Atoms/cm 3, target resistivity is phosphorus element content ω in the silicon single-crystal of 28 Ω .cm Target=1.56 * 10 14Atoms/cm 3, doping agent alloy phosphorus element content ω Alloy=3.53 * 10 17Atoms/cm 3Therefore, required doping agent alloy mass can obtain M by following formula (1) Alloy=23.8g (promptly doped alloys quality) first.
2. the raw material for preparing is put in the Kayex CG6000 type vertical pulling stove; The heatingization material; After the change material finishes, heating power is adjusted to seeding power (this embodiment seeding power is 55kw), set seeding temperature spot (this embodiment seeding temperature spot is 1450 SP); Under this temperature, stable silicon liquation 10 minutes.
3. the drawing of test monocrystalline: test the drawing of monocrystalline according to the method among the embodiment 1, the thin neck length degree of seeding is 3.8cm among this embodiment, and the thin neck diameter of seeding is 3.3mm; The isometrical diameter of test silicon monocrystalline is 3cm (optimum diameter is 3cm); Etc. electrical path length is 4.5cm, the operation that finishes up at last, and epilog should slowly be carried out; Make afterbody become taper, it is pointed that tail end becomes.
4. the processing of specimen: the test silicon monocrystalline is taken out, after cooling finishes, the surface is processed with oilstone; The arc surface of choosing test monocrystalline equal-diameter part grinds into the plane with it, and the planar size is advisable to be fit to the test of four point probe resistivity tester, is generally 5mm * 5mm size; To test monocrystalline rotation proper angle then; Grind next test plane, so grind plane 2-3 of test, grind 3 on plane in the present embodiment altogether.
5. the specimen of completion of processing is carried out resistivity measurement; The test position is the plane of above-mentioned processing; Each plane test three times; Get the MV and the record of three secondary flat test datas, it is following to survey three planar average resistivity data in the present embodiment: 44 Ω .cm, 43.8 Ω .cm, 43.8 Ω .cm, get the resistivity value of the MV 43.9 Ω .cm of above-mentioned three data as this specimen again.
6. can be known by above test that specimen resistivity value 43.9 Ω .cm and target resistivity are worth 28 Ω .cm and differ 15.9 Ω .cm, phase difference>5 Ω .cm does not reach the product parameters requirement, need carry out the second time and mix.The content of phosphoric equates with the content of phosphoric in the existing silicon melt in the known prepared specimen; Therefore can draw the content of phosphoric in the silicon melt by the resistivity value of specimen; Same according to the method in the preparation raw material step, according to being numbered the content ω that GB/T 13389-92 " phosphorus single crystal silicon resistivity and concentration of dopant conversion rules are mixed in boron-doping " national standard can calculate phosphoric in silicon melt this moment Melt=9.83 * 10 13Atoms/cm 3, secondly can know phosphorus element content ω in institute's doped alloys Alloy=3.53 * 10 17Atoms/cm 3, phosphorus element content ω in the target melt Target=1.56 * 10 14Atoms/cm 3, melt quality can approximate batching quality, i.e. M Melt≈ M Polycrystalline+ M AlloySo=55kg is by following formula (M Polycrystalline+ M Alloy) * ω Target– M Melt* ω Melt=M Secondary alloy* ω AlloyCalculating can obtain: M Secondary alloy=8.99g.
7. adjustment silicon liquid temp carries out the silicon bowl and draws, after the preparation of silicon bowl finishes; Close plate valve in the stove,, open fire door last furnace chamber inflation; Load weighted doped alloys 8.99g is put in the silicon bowl, closes fire door and carry out replacement operator, after displacement finishes; The silicon bowl that carries doped alloys is immersed in the silicon liquid, accomplish for the second time and mix.
8. after secondary doping finishes, carry out steady temperature operation once more, set seeding temperature spot (this embodiment seeding temperature spot is 1450 SP), under this temperature, stable silicon liquid temp 10 minutes.
9. afterwards; Carry out the drawing of test silicon monocrystalline, the processing of specimen, the resistivity measurement of specimen once more according to above-mentioned the 1st~5 step; The resistivity value that finally obtains the specimen behind the secondary doping is 33.2 Ω .cm; Be worth 28 Ω .cm with the silicon single-crystal target resistivity and differ 5.2 Ω .cm, phase difference>5 Ω .cm does not satisfy the requirement of silicon single-crystal target resistivity.
10. because the discontented sufficient requirement of above-mentioned resistivity difference, thus to mix for the third time, same according to above-mentioned method of calculation, doped alloys quality is for the third time calculated: M Three alloys=3.74g.
After 11. doping finishes for the third time; According to above-mentioned the 1st~5 step; Carry out operations such as steady temperature, test single crystal preparation, specimen processing once more, finally obtaining this specimen resistivity is 28.8 Ω .cm, is worth 28 Ω .cm with the silicon single-crystal target resistivity to differ 0.8 Ω .cm; Phase difference<5 Ω .cm satisfies the requirement of silicon single-crystal target resistivity.
12., can know that the P constituent content is 1.5 * 10 in melt this moment according to the 28.8 Ω .cm of the specimen resistivity value behind the above secondary doping 14Atoms/cm 3, and can judge that thus the melt after the doping satisfies the requirement that draws the finished product single crystal silicon resistivity, so operation afterwards can be prepared the finished silicon monocrystalline that resistivity meets the demands according to the czochralski silicon monocrystal preparation technology of routine.

Claims (1)

1. a method of controlling the czochralski silicon monocrystal head resistivity is characterized in that comprising the steps:
Step 1. raw material carries out the drawing of test silicon monocrystalline after all melting and finishing; The length of test silicon crystal-pulling is answered >=6cm, and the length of test silicon crystal-pulling comprises shouldering part, equal-diameter part and ending part, and wherein the equal-diameter part diameter is 2cm~3cm, equal-diameter part length >=4cm;
Step 2. after the test silicon crystal-pulling finishes, take out the test silicon monocrystalline, test silicon single-wafer cylinder partial is processed into the plane, obtain specimen;
Step 3. afterwards, the planar section of specimen is carried out resistivity measurement with the four point probe resistivity tester, and record resistivity measurement value;
Step 4. the resistivity measurement value of compare test sample and silicon single-crystal target resistivity value; Calculate the resistivity measurement value of specimen and the difference of silicon single-crystal target resistivity; If the resistivity measurement value of specimen is than silicon single-crystal target resistivity value >=5 Ω .cm; Then carry out the operation of following steps, otherwise the resistivity measurement value of specimen satisfies the requirement of silicon single-crystal target resistivity, directly carries out normal pulling operation;
Step 5. according to the resistivity measurement value of specimen and the difference of silicon single-crystal target resistivity value, calculate required doped alloys quality;
Step 6. the doped alloys that will calculate certain mass mixes in the silicon melt;
Step 7. after the complete melt-blended of doped alloys is even, repeats step 1 to step 3, and calculate the resistivity measurement value of specimen and the difference of silicon single-crystal target resistivity value once more;
Step 8. if the resistivity measurement value of calculating the gained specimen for the second time is than silicon single-crystal target resistivity value >=5 Ω .cm; Then repeat step 5 to step 7; Until the resistivity measurement value of specimen than silicon single-crystal target resistivity value<5 Ω .cm; Then stop to mix, the resistivity of specimen satisfies the requirement of silicon single-crystal target resistivity, promptly accomplishes the control of silicon single-crystal head resistivity.
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