CN101994099B - Method for forming fluorine-doped silicon oxide thin film - Google Patents

Method for forming fluorine-doped silicon oxide thin film Download PDF

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CN101994099B
CN101994099B CN200910194445A CN200910194445A CN101994099B CN 101994099 B CN101994099 B CN 101994099B CN 200910194445 A CN200910194445 A CN 200910194445A CN 200910194445 A CN200910194445 A CN 200910194445A CN 101994099 B CN101994099 B CN 101994099B
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silicon oxide
fluorine
standard cubic
cubic centimeters
oxide film
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CN101994099A (en
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牟善勇
田守卫
姜国伟
熊辉
刘玮
解毅
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Shanghai Huahong Grace Semiconductor Manufacturing Corp
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Shanghai Huahong Grace Semiconductor Manufacturing Corp
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Abstract

The invention relates to a method for forming a fluorine-doped silicon oxide thin film, which comprises the following steps: providing a chemical vapor deposition device for implementing the cleaning step for a reaction chamber of the chemical vapor deposition device; forming a covering layer on the surface of the reaction chamber, wherein the covering layer has different thicknesses in different positions of the chamber, and the thickness of the covering layer corresponds to the rate of thinning the covering layer of fluorine ions in the different positions of the reaction chamber; and providing a substrate, and forming the fluorine-doped silicon oxide thin film on the surface of the substrate in the chamber formed with the covering layer. The method can reduce the number of defects on the surface of the fluorine-doped silicon oxide thin film and improve the efficiency of the process for forming the fluorine-doped silicon oxide thin film.

Description

Mix the formation method of the silicon oxide film of fluorine
Technical field
The present invention relates to field of semiconductor manufacture, particularly a kind of formation method of mixing the silicon oxide film of fluorine.
Background technology
In VLSI technology, the silicon-dioxide that thermostability, moisture resistance are arranged is the main insulating material that metal interconnected circuit chien shih is used always, and metallic aluminium then is the main raw of circuit interconnection lead in the chip.Yet; With respect to the microminiaturization of element and the increase of integrated level; Conductor line number constantly increases in the circuit; Make resistance (R) and electric capacity (C) in the conductor line framework produce ghost effect, cause serious transport delay (RC Delay), reaching in the more advanced technology in 130 nanometers becomes the limited principal element of signal transmission speed in the circuit.
Therefore, the prior art dielectric materials that in semiconductor technology, adopts new low electrical resistant material copper and low-k like the silicon oxide (FSG, Fluorine-doped Silicon Dioxide) of mixing fluorine to reduce transport delay.
The said silicon oxide of mixing fluorine adopts high density plasma chemical vapor deposition (High DensityPlasma Chemical Vapor Deposition usually; HDP CVD) forms; The major advantage of high density plasma chemical vapor deposition is can be under lower depositing temperature; Prepare the silicon oxide film of mixing fluorine, but the silicon oxide film of mixing fluorine that said employing high density plasma chemical vapor deposition forms at substrate surface, and the surface can form a large amount of defectives usually.
Summary of the invention
The problem that the present invention solves is to reduce the defects count on the silicon oxide film surface of mixing fluorine.
For addressing the above problem; The present invention provides a kind of formation method of mixing the silicon oxide film of fluorine; Comprise: chemical vapor depsotition equipment is provided; Reaction chamber surface at said chemical vapor depsotition equipment forms tectum, and said tectum is different at the different position thickness of chamber, and said tectal thickness is corresponding in the different tectal speed of position attenuate of reaction chamber with fluorion; Substrate is provided, is formed with in the tectal chamber, form the silicon oxide film of mixing fluorine at substrate surface said
Compared with prior art; The present invention has the following advantages: mix in formation before the silicon oxide layer of fluorine; Form tectum on said reaction chamber surface; Said tectum is different at the different position thickness of chamber, and said tectal thickness is corresponding in the different tectal speed of position attenuate of reaction chamber with fluorion, and said tectum is two-layer or two-layer above stacked structure; Make tectum mix in the silicon oxide layer technology of fluorine in formation; The tectum that the reaction chamber surface local can not occur is corroded and exhausts; And then expose the phenomenon of the ceramic alumina of chamber surfaces, thus the defects count of in the silicon oxide layer technology of fluorine is mixed in formation, mixing the silicon oxide layer surface of fluorine reduced, on the other hand; Owing to being corroded, the tectum that the reaction chamber surface local can not occur exhausts; And then exposing the ceramic alumina of chamber surfaces, said tectal formation frequency also can reduce, thereby has improved the efficient that forms the silicon oxide layer of mixing fluorine.
Description of drawings
Fig. 1 is the schematic flow sheet of the formation method of the silicon oxide film of mixing fluorine of the present invention;
Fig. 2 forms tectal synoptic diagram on the reaction chamber surface in the formation method of the silicon oxide film of mixing fluorine of the present invention;
Fig. 3 is the substrate synoptic diagram that provides in the formation method of the silicon oxide film of mixing fluorine of the present invention;
Fig. 4 is the synoptic diagram that on substrate shown in Figure 3, forms the silicon oxide film of mixing fluorine.
Embodiment
Can know by background technology; The silicon oxide film surface of mixing fluorine that existing technology forms can form a large amount of defectives usually; Making has adopted the integrated circuit technology yield of the silicon oxide film technology of mixing fluorine lower; Contriver of the present invention is through a large amount of experiments, and it is because the silicon oxide film surface of mixing fluorine that forms is formed with particle contamination that discovery has adopted the integrated circuit technology yield of the silicon oxide film technology of mixing fluorine low.
The contriver further discovers; The silicon oxide film technology of mixing fluorine of said formation adopt usually chemical vapour deposition (Chemical Vapor Deposition, CVD) equipment carries out, the substrate of needs depositions being mixed the silicon oxide film of fluorine is positioned over the chamber of chemical vapor depsotition equipment and the silicon oxide film that deposition is mixed fluorine; Said chamber adopts the ceramic alumina preparation to form usually; Mix in the silicon oxide film process of fluorine in deposition, fluorion can react with the ceramic alumina of chamber, forms the compound impurity that contains aluminium and fluorine; Said impurity is mixed in the silicon oxide film process of fluorine and can be formed defective at substrate surface in deposition, and said defective is a kind of of particle contamination.
For this reason, existing deposition is mixed the silicon oxide film technology of fluorine can be before deposition be mixed the silicon oxide film of fluorine, carries out in chamber surfaces and forms the tectum step; Thereby make that when deposition is mixed the silicon oxide film of fluorine fluorion can directly not contact the ceramic alumina of chamber, reduced the silicon oxide film process of mixing fluorine forms defective at substrate surface quantity; But contriver of the present invention finds that through a large amount of work the existing tectum that is formed on chamber surfaces is the period to cover one deck tectum in chamber surfaces, and said tectum can't accurately be controlled at the not comprovincial thickness of chamber; Said tectum homogeneity is bad, and is briefly, thicker in some local tectum meeting of chamber; Can be thinner at some local tectum, and when deposition is mixed the silicon oxide film of fluorine, fluorion meeting attenuate tectum; In the thin place of tectum; Can be easy to expose the alumina-ceramic of chamber, can be known by narration before, fluorion can react with the ceramic alumina of chamber; Form the compound impurity of aluminium and fluorine, the silicon oxide film defects count that causes mixing fluorine rises.Contriver of the present invention further finds, mixes in the process of silicon oxide film of fluorine in deposition, and fluorion attenuate tectum is at the chamber different positions; The speed of attenuate can be different, and the place that fluorion attenuate speed is fast is easy to just expose the ceramic alumina of chamber; Same; Fluorion can react with the ceramic alumina of chamber, forms the compound impurity of aluminium and fluorine, and the silicon oxide film defects count that causes mixing fluorine rises.
For this reason, the present invention proposes a kind of formation method of mixing the silicon oxide film of fluorine, has set forth a lot of details in the following description so that make much of the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar popularization under the situation of intension of the present invention, so the present invention does not receive the restriction of following disclosed practical implementation.
Secondly, the present invention utilizes synoptic diagram to be described in detail, when the embodiment of the invention is detailed; For ease of explanation; The sectional view of expression device architecture can be disobeyed general ratio and done local the amplification, and said synoptic diagram is instance, and it should not limit the scope of the present invention's protection at this.The three-dimensional space size that in actual fabrication, should comprise in addition, length, width and the degree of depth.
Fig. 1 is the schematic flow sheet of the formation method of the present invention's silicon oxide film of mixing fluorine, specifically comprises the steps:
Step 101 provides chemical vapor depsotition equipment, and the reaction chamber of chemical vapor depsotition equipment is carried out cleaning;
Step 102; Form tectum on said reaction chamber surface; Said tectum is different at the different position thickness of chamber, and said tectal thickness is corresponding in the different tectal speed of position attenuate of reaction chamber with fluorion, and said tectum is two-layer or two-layer above stacked structure;
Step 103 provides substrate, is formed with in the tectal chamber said, forms the silicon oxide film of mixing fluorine at substrate surface.
Below in conjunction with accompanying drawing, formation method of mixing the silicon oxide film of fluorine of the present invention is elaborated.
Of step 101; Chemical vapor depsotition equipment is provided; In the present embodiment; Said chemical vapor depsotition equipment is a high density plasma chemical vapor deposition equipment, and what need particularly point out is that the chemical vapor depsotition equipment that can form the silicon oxide film of mixing fluorine all falls into the spirit and scope of the present invention.
Said chemical vapor depsotition equipment is used to form the silicon oxide film of mixing fluorine; In existing technology, in the process of using the chemical vapor depsotition equipment deposit film, in the film forming while of substrate surface; Also can form attachment film in chamber surfaces; Said attachment film deposits to certain thickness, and the particle of attachment film can drop in deposition process at substrate surface, forms defective; Usually after the film of the certain number of times of deposition, can carry out cleaning; Said cleaning is formed on the attachment film on reaction chamber surface in order to removal.
The principle of said cleaning is for adopting the reaction of fluorion and attachment film; Be formed on the attachment film on reaction chamber surface with removal; The concrete parameter of said cleaning is: reaction chamber pressure is 4 millitorr to 5 millitorrs, and reaction power is 4000 watts, and reactant gases is NF 3, assist gas is Ar, NF 3Flow is PM 1000 standard cubic centimeters to PM 2000 standard cubic centimeters, and the Ar flow is PM 0 standard cubic centimeter to PM 2000 standard cubic centimeters.
Existing technology can be after carrying out cleaning, and at formation one deck tectum of chamber surfaces, said tectum can't accurately be controlled at the not comprovincial thickness of chamber; Mix in the silicon oxide film step of fluorine in follow-up formation, fluorion attenuate tectum is at the chamber different positions, and the speed of attenuate can be different; The place that fluorion attenuate speed is fast; Be easy to just expose the ceramic alumina of chamber, same, fluorion can react with the ceramic alumina of chamber; Formation contains the compound impurity of aluminium and fluorine, and the silicon oxide film defects count that causes mixing fluorine rises.
To this; With reference to figure 2, the present invention forms tectum 20 on said reaction chamber 10 surfaces, and said tectum 20 materials are selected from silicon oxide; Said tectum 20 is different at the different position thickness of chamber; Said tectal thickness and fluorion are corresponding in the speed of the different position attenuate tectum 20 of chamber 10, in the high zone of chamber 10 surperficial fluorion attenuate tectum 20 speed, the thicker of tectum 20; At the low zone of chamber 10 surperficial fluorion attenuate tectum 20 speed, the thin thickness of tectum 20.
Said fluorion can provide also tectum 20 experiment tests of the different position of fluorion attenuate chamber 10 that can be through reality to obtain by the equipment supplier in the speed of the different position attenuate tectum 20 of chamber 10.
Said fluorion can form tectum 20 on chamber 10 surfaces at chamber 10 different position attenuate tectum 20 experiment tests; Carry out and form the silicon oxide film technology of mixing fluorine; Cover the thickness thinning of chamber 10 surface coatings 20 through test, obtain the speed of fluorion attenuate tectum 20.
In order to form said thickness and the fluorion corresponding tectum 20 of speed at the different position attenuate tectum 20 of chamber 10, said tectum 20 is two-layer or two-layer above stacked structure.
What need particularly point out is, forming the said thickness tectum 20 corresponding with the speed of fluorion attenuate tectum 20 can also be through the control reaction pressure, reaction power, and reaction gas flow is realized.
In the present embodiment, said formation tectum 20 is the first layer tectum 21 and second tectum, 22 overlaying structures, and said the first layer tectum 21 forms processing parameter and does; Reaction chamber pressure is 50 millitorrs; The top reaction power is 2500 to 4000 watts, and the sidewall reaction power is 0 to 2000 watt, SiH 4Flow is PM 150 standard cubic centimeters to PM 200 standard cubic centimeters, and the Ar flow is PM 100 standard cubic centimeters to PM 200 standard cubic centimeters, O 2Flow is PM 250 standard cubic centimeters to PM 350 standard cubic centimeters, and the reaction times is 10 seconds to 30 seconds; It is that reaction chamber pressure is 5 to 20 millitorrs that said second layer tectum 22 forms processing parameter; The top reaction power is 1000 to 3000 watts; The sidewall reaction power is 1000 to 4000 watts; The SiH4 flow is PM 150 standard cubic centimeters to PM 200 standard cubic centimeters, and the Ar flow is PM 100 standard cubic centimeters to PM 200 standard cubic centimeters, O 2Flow is PM 250 standard cubic centimeters to PM 350 standard cubic centimeters, and the reaction times is 10 seconds to 30 seconds.
Of step 103; With reference to figure 3 substrate 100 is provided; Said substrate 100 can be substrate (part that comprises unicircuit and other elements), the patterning of multi layer substrate (silicon substrate that for example, has covering dielectric and metallic membrane), classification substrate, silicon-on-insulator substrate (SOI), epitaxial silicon substrate, partially disposed or the substrate that is not patterned.
With reference to figure 4, said substrate 100 is written in the chamber, form the silicon oxide layer 200 of mixing fluorine on substrate 100 surfaces.
The concrete technology that the silicon oxide layer 200 of fluorine is mixed in said formation is: reaction chamber pressure is 5 millitorr to 8 millitorrs, and the top reaction power is 1000 watts to 2000 watts, and the sidewall reaction power is 2000 watts to 3000 watts, and bottom power is 2000 watts to 3000 watts, SiH 4Flow is PM 20 standard cubic centimeters to PM 60 standard cubic centimeters, oxygen (O 2) flow is PM 100 standard cubic centimeters to PM 150 standard cubic centimeters, SiF 4Flow is PM 20 standard cubic centimeters to PM 60 standard cubic centimeters.
The present invention is through before the silicon oxide layer 200 of mixing fluorine in formation; Form tectum on said reaction chamber surface; Said tectum is different at the different position thickness of chamber; Said tectal thickness is corresponding with the tectal speed of fluorion attenuate, and said tectum is two-layer or twice above stacked structure; Make tectum mix in silicon oxide layer 200 technologies of fluorine in formation; The tectum that the reaction chamber surface local can not occur is corroded and exposes the ceramic alumina of chamber surfaces; Thereby reduced the defects count on silicon oxide layer 200 surfaces of in silicon oxide layer 200 technologies of fluorine are mixed in formation, mixing fluorine; On the other hand; Expose the ceramic alumina of chamber surfaces owing to the tectum that the reaction chamber surface local can not occur is corroded, said tectal formation frequency also can reduce, thereby has improved the efficient that forms the silicon oxide layer 200 of mixing fluorine.
Though the present invention discloses as above with preferred embodiment, the present invention is defined in this.Any those skilled in the art without departing from the spirit and scope of the present invention, all can do various changes and modification, so protection scope of the present invention should be as the criterion with claim institute restricted portion.

Claims (12)

1. a formation method of mixing the silicon oxide film of fluorine is characterized in that, comprising:
Chemical vapor depsotition equipment is provided;
Reaction chamber surface at said chemical vapor depsotition equipment forms tectum, and said tectum is different at the different position thickness of chamber, and said tectal thickness is corresponding in the different tectal speed of position attenuate of reaction chamber with fluorion;
Substrate is provided, is formed with in the tectal chamber, form the silicon oxide film of mixing fluorine at substrate surface said.
2. formation method of mixing the silicon oxide film of fluorine as claimed in claim 1 is characterized in that, said formation method of mixing the silicon oxide film of fluorine also comprises carries out cleaning to the reaction chamber of chemical vapor depsotition equipment.
3. formation method of mixing the silicon oxide film of fluorine as claimed in claim 2 is characterized in that, the concrete parameter of said cleaning is: reaction chamber pressure is 4 millitorr to 5 millitorrs, and reaction power is 4000 watts, and reactant gases is NF 3, assist gas is Ar, NF 3Flow is PM 1000 standard cubic centimeters to PM 2000 standard cubic centimeters, and the Ar flow is PM 0 standard cubic centimeter to PM 2000 standard cubic centimeters.
4. formation method of mixing the silicon oxide film of fluorine as claimed in claim 1 is characterized in that said chemical vapor depsotition equipment is a high density plasma chemical vapor deposition equipment.
5. formation method of mixing the silicon oxide film of fluorine as claimed in claim 1 is characterized in that said covering layer material is selected from silicon oxide.
6. formation method of mixing the silicon oxide film of fluorine as claimed in claim 1 is characterized in that, said tectal formation technology is chemical vapor deposition method.
7. formation method of mixing the silicon oxide film of fluorine as claimed in claim 1 is characterized in that, said tectum forms in same apparatus cavity with the silicon oxide film of mixing fluorine.
8. formation method of mixing the silicon oxide film of fluorine as claimed in claim 1 is characterized in that, said tectum is two-layer above stacked structure.
9. formation method of mixing the silicon oxide film of fluorine as claimed in claim 7 is characterized in that said tectum comprises first tectum and second tectum.
10. formation method of mixing the silicon oxide film of fluorine as claimed in claim 9 is characterized in that, said first tectum forms processing parameter and does; Reaction chamber pressure is 50 millitorrs; The top reaction power is 2500 to 4000 watts, and the sidewall reaction power is 0 to 2000 watt, SiH 4Flow is PM 150 standard cubic centimeters to PM 200 standard cubic centimeters, and the Ar flow is PM 100 standard cubic centimeters to PM 200 standard cubic centimeters, O 2Flow is PM 250 standard cubic centimeters to PM 350 standard cubic centimeters, and the reaction times is 10 seconds to 30 seconds.
11. formation method of mixing the silicon oxide film of fluorine as claimed in claim 9; It is characterized in that it is that reaction chamber pressure is 5 to 20 millitorrs that said second tectum forms processing parameter, the top reaction power is 1000 to 3000 watts; The sidewall reaction power is 1000 to 4000 watts, SiH 4Flow is PM 150 standard cubic centimeters to PM 200 standard cubic centimeters, and the Ar flow is PM 100 standard cubic centimeters to PM 200 standard cubic centimeters, O 2Flow is PM 250 standard cubic centimeters to PM 350 standard cubic centimeters, and the reaction times is 10 seconds to 30 seconds.
12. formation method of mixing the silicon oxide film of fluorine as claimed in claim 1; It is characterized in that; The concrete parameter that the silicon oxide film of fluorine is mixed in formation is: reaction chamber pressure is 5 millitorr to 8 millitorrs, and the top reaction power is 1000 watts to 2000 watts, and the sidewall reaction power is 2000 watts to 3000 watts; Bottom power is 2000 watts to 3000 watts, SiH 4Flow is PM 20 standard cubic centimeters to PM 60 standard cubic centimeters, and oxygen flow is PM 100 standard cubic centimeters to PM 150 standard cubic centimeters, SiF 4Flow is PM 20 standard cubic centimeters to PM 60 standard cubic centimeters.
CN200910194445A 2009-08-17 2009-08-17 Method for forming fluorine-doped silicon oxide thin film Active CN101994099B (en)

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CN102456568A (en) * 2011-09-29 2012-05-16 上海华力微电子有限公司 Method for deposition of nitrogen-doped silicon carbide film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6071573A (en) * 1997-12-30 2000-06-06 Lam Research Corporation Process for precoating plasma CVD reactors
US6403501B1 (en) * 2000-12-27 2002-06-11 Novellus Systems, Inc. Method of controlling FSG deposition rate in an HDP reactor
CN101208457A (en) * 2005-06-29 2008-06-25 Oc欧瑞康巴尔斯公司 Method for manufacturing flat substrates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6071573A (en) * 1997-12-30 2000-06-06 Lam Research Corporation Process for precoating plasma CVD reactors
US6403501B1 (en) * 2000-12-27 2002-06-11 Novellus Systems, Inc. Method of controlling FSG deposition rate in an HDP reactor
CN101208457A (en) * 2005-06-29 2008-06-25 Oc欧瑞康巴尔斯公司 Method for manufacturing flat substrates

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