CN1424745A - Single-step clean method for diffuse and oxidation process - Google Patents
Single-step clean method for diffuse and oxidation process Download PDFInfo
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- CN1424745A CN1424745A CN 03114701 CN03114701A CN1424745A CN 1424745 A CN1424745 A CN 1424745A CN 03114701 CN03114701 CN 03114701 CN 03114701 A CN03114701 A CN 03114701A CN 1424745 A CN1424745 A CN 1424745A
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Abstract
An one-step washing method for diffusing or oxidizing technology features use of washing solution HHSCIAC-clean prepared from APM, TMAH and EDTA. Its advantages are high clean quality and high stability.
Description
Technical field
The invention belongs to field of IC technique, be specifically related to that a kind of new being used to spread, the single step pre-cleaning method of oxidation technology.
Background technology
Since the invention of the eighties of last century semiconductor transistor fifties, particularly the birth of initial stage sixties silicon planner technology and epitaxy technology makes process for fabrication of semiconductor device obtain important breakthrough.Integrated circuit industry arises at the historic moment subsequently.Since the solid state device technology occurs simultaneously, it has been recognized that clean substrate surface importance in the semiconductor microactuator electronic device is made.Device performance, reliability and silicon circuit finished product rate are subjected to remaining in silicon chip or device surface chemical reagent impurity and granule foreign and have a strong impact on as everybody knows.Because semiconductor surface and submicron-scale device feature extreme sensitivity are cleaned effective technology even are seemed more important than cleaning before behind initially cleaning of silicon chip, oxidation and the formation figure.Therefore, super cleaning silicon wafer surface preparation is in very lagre scale integrated circuit (VLSIC) (VLSI) silicon circuit is produced, and for example 64-and 256M DRAM device have become one of key technology." super cleaning " can be defined as the term of silicon face chemical impurity and granule density, and ben is that total in general metal impurities should be less than 10
10Atom/cm
2Greater than 0.1 micron particles, should be less than 0.1/cm
2, that is to say diameter is less than 31 particles for the 200mm silicon chip.In fact these very low amount of impurities make us unthinkable! And these are strictly regulated and just are based on the following fact: the entire device quality as mentioned above, is influenced by trace impurity seriously.Hundreds of each step of processing step all may cause contamination in advanced silicon integrated circuit manufacture process.For example for 64 and 256M DRAM or be equal to the integration density circuit in the whole production manufacture process, nearly 60 to 75 steps of matting clean, and account for 15% of total manufacturing technology steps.
Organic and inorganic and particulate contamination on the silicon chip surface normally is incorporated into silicon chip surface with chemistry or physical adsorption way or is embedded in the silicon chip surface autoxidation film.These contamination impurity and particulate contamination can have a strong impact on performance, rate of finished products and the reliability of device.Experiment shows have the substandard products above 50% to cause owing to cleaning not little at once contamination, thereby make the ultra-clean surface preparation technology become to make the key process technology of extensive (LSI) and ultra-large (VLSI) integrated circuit (IC).So-called ultra-clean surface requires promptly that silicon chip surface does not have particulate contamination, organic pollutant, metal contamination thing, no natural oxide, hydrogen terminal or complete ultra-thin chemical oxide, surface microroughness will be little etc. fully.According to ITRS Roadmap in 2000, be example with 0.18 micron VLSI CMOS IC process for making, preceding road technology integrated to the cleaning specification requirement referring to shown in the Table I.
Table I: the part of ITRS Roadmap in 2000
| Technology generation | 180nm |
| Granule number is (individual/cm 2) | 0.325 |
| Granular size (nm) | 82.5 |
| Surface metal concentration (atom/cm 2) | 7E9 |
| Movable concentration of metal ions (atom/cm 2) | 4.25E10 |
| Organic/polymeric impurities (carbon atom/cm 2) | 6.6E13 |
| Surface microroughness (nm) | 0.14 |
This shows, must remove effectively during cleaning the surface organic and inorganic pollutant, and don't the erosion and destroy silicon chip surface or cause surface roughening.
What generally adopt in the world semiconductor integrated circuit production at present is that Werner Kern is applied in the production of RCA silicon semiconductor device in the nineteen sixty-five research and development, and delivers RCA standard cleaning method in 1970.Afterwards, people find that in the semiconductor integrated circuit production process there are many shortcomings in RCA standard cleaning method.Therefore, RCA standard cleaning method constantly is improved and is perfect.
The conventional clean process is: at first use sulfuric acid (H
2SO
4)/hydrogen peroxide (H
2O
2), being called for short SPM, ratio is the 3/1-10/1 mixed solution, cleans under high temperature 100-130 ℃ condition, main purpose is to remove organic substance and/or photoresist.Then need hot water to carry out rinsing, remove residue.Second step adopted 1-2% diluted hydrofluoric acid (dHF) to remove oxide layer.Adopt typical R CA cleaning then, promptly a standard cleaning solution (SC1) (also claiming APM) cleans, and after the high purity water rinsing, and then uses No. two standard cleaning solution (SC2) to clean, and carries out rinsing and drying at last.
Adopt SPM to clean following shortcoming is arranged: use a large amount of sulfuric acid and hydrogen peroxide, need a large amount of hot water to carry out rinsing repeatedly and remove various residues, yet experimental results show that from the teeth outwards still has " sulphur " residue.The sulfuric acid waste disposal is another shortcoming.Otherwise serious environment pollution.Several new methods, for example sulfuric acid (H have been developed at present
2SO
4)/ozone (O
3) be called for short SOM, and ozone (O
3)/DI water replaces SPM.These two kinds of cleaning solutions only need several ppm (1,000,000/) ozone.Particularly ozone/DI glassware for drinking water has or not sulphur production, does not have environmental pollution, and advantage such as reduce production costs simultaneously greatly.
APM has been widely used in the manufacturing of Si semiconductor integrated circuit.A large amount of experiments have proved that APM has excellent particle removal ability, as shown in Figure 1.Yet APM mixing cleaning solution does not obtain fine optimization for clean metal impurity.When there are metal impurities in rinse bath, owing to metal impurities catalysis decomposing hydrogen dioxide solution causes cleaning solution minimizing in useful life, as shown in Figure 2.Have been found that particularly the harmfulness that exists of metallic iron and a little copper is very large.And in cleaning process, have the trace meter risk of contamination, and for example metal impurities iron, nickel, zinc and al deposition are to silicon chip surface, and Fig. 3 is an example.Therefore, make metal surface impurity be difficult to remove.Because existing, metal impurities such as iron cause wafer surface slightly poor simultaneously.Effectively clean, remove metal impurities in order to improve APM, can add complexometric reagent or surface-active agents.Just because of above-mentioned factors, need to adopt HPM mixing cleaning solution to carry out subsequent technique and clean.
Summary of the invention
The objective of the invention is to propose a kind of new diffusion, oxidation technology pre-cleaning method of being used for, used a kind of new cleaning formulation, only needed to clean and to realize above-mentioned multistep cleaning performance, called after HHSC1AC-Clean once the step.
The present invention proposes is used to spread, the single step pre-cleaning method of oxidation technology, its cleaning fluid is based on APM solution, its ammoniacal liquor: hydrogen peroxide: the volume ratio of deionized water is 1: 3 ~ 5: 15 ~ 25, the temperature of solution is 40-80 ℃, the single step scavenging period is 3 to 15 minutes, carry out HF after the prerinse and clean, follow rinsing and drying then.
Among the present invention, on above-mentioned APM solution ratio basis, can add tetramethyl oxyammonia (TMAH) and complexometric reagent (CA) ethylenediamine tetra-acetic acid (EDTA), the temperature of mixed solution is 40-80 ℃, the single step scavenging period is 3 to 15 minutes, carry out HF (hydrofluoric acid) after the prerinse and clean, carry out rinsing and drying then.
The pre-cleaning method that the present invention proposes is adapted at before initial oxidation, gate oxidation, N trap and the operations such as the propelling of P trap, thin film deposition wafer being carried out prerinse.In addition, the present invention also is adapted at various implantation dosages (as N trap, P trap, N
+, P
+Inject) dry method operation such as remove photoresist cleans after finishing.
Contain ammoniacal liquor (29%NH in the above-mentioned mixed solution
3H
2O), content is 3-5%; Contain TMAH (2.38%) TMAH in the above-mentioned mixed solution, content is 400-2000ppm; Contain EDTA in the above-mentioned mixed solution, content is 50-200ppm.Contain hydrogen peroxide (30%H in the above-mentioned mixed solution
2O
2), content is 10-25%; The content of DIW is 85-70% in the above-mentioned mixed solution.
The principle of the invention is, on very rare APM mixed solution basis, adds tetramethyl oxyammonia (TMAH) and complexometric reagent EDTA, and the effect of adding TMAH is because molecular volume is big more a lot of than ammoniacal liquor, avoided traditional APM to cause the surface problem that slightly is pickled with grains or in wine like this.Add complexometric reagent CA effect and be remedy ammoniacal liquor can't some metal ion shortcoming of complexing, abilities such as complexometric reagent CA complexing metal iron, nickel, zinc and aluminium are strong especially.
The present invention proposes is used for diffusion, oxidation technology single step pre-cleaning method, in preceding road technology integrated (FEOL) manufacture process, before many diffusions, oxidation technology, can clean, also can be used in and clean after various dosage injection dry method are removed photoresist with this method.Characteristics are very rare mixed solutions.Has following advantage: high particle removal efficiency; Low metal impurities remnants; Good micro-content organism is removed efficient; The surface microroughness is very little; Reduce chemical reagent/DI water consumption; Reduce waste disposal; Shorten the explained hereafter time greatly; Improve output; Less occupation area of equipment; Reduce production costs; Very good technology stability; Improve environment, safety and health (ESH) performance.
Description of drawings
Fig. 1 is that different chemical composition ratio SC1 removes the particulate efficiency schematic diagram.Illustrate: DIW represents ultra-pure water, and ME represents to use million acoustic vibration energy, and A, B, C represent three kinds of different chemical composition ratio SC1 mixed solutions.
Fig. 2 is SC1 existing problems under 70 ℃ of conditions: ammonia (NH
3H
2O) volatilization and hydrogen peroxide (H
2O
2) decomposing schematic representation.As seen from Figure 2, in ultrapure chemical reagent, ammonia volatilization is more faster than decomposing hydrogen dioxide solution.
Fig. 3 is that metallic iron stains problem: silicon chip soaked 10 minutes in 70 degree SC1.Concentration is the log-linear relation in metallic iron surface concentration and the solution as seen from Figure 3!
Fig. 4 is the EDTA schematic arrangement.
Fig. 5 is that big molecule TMAH reduces a kind of mechanism schematic diagram of surperficial microroughness.
Embodiment
The concrete implementation step that the invention is further illustrated by the following examples.
The preparation of first step cleaning solution:
1, measures deionized water DI water (volume ratio is 70%) with graduated cylinder, pour in the clean Sheng solution rinse bath.
2, accurately measure 50ppm EDTA with graduated cylinder, slowly pour in the above-mentioned Sheng high purity water rinse bath.
3, accurately measure TMAH with graduated cylinder, content is 0.04%, slowly pours in above-mentioned Sheng 1,2 rinse baths.
4, measure a certain amount of 30% hydrogen peroxide (volume ratio is 20%) with graduated cylinder, slowly pour in above-mentioned Sheng 1,2,3 rinse baths.
5, measure a certain amount of ammoniacal liquor (29%NH with graduated cylinder
3H
2O), content is 3%, slowly pours in above-mentioned Sheng 1,2,3,4 rinse baths.
6, above-mentioned 1 to 5 the step finish after, allow various compositions mix, stand-by.
7, cleaning solution is heated to the temperature of technological requirement.
The second step cleaning:
1, before operations such as initial oxidation, gate oxidation, N trap and the propelling of P trap, wafer is carried out prerinse respectively;
2, respectively at various implantation dosages (as N trap, P trap, N
+, P
+Inject) dry method operation such as remove photoresist cleans after finishing.
3, scavenging period is decided as the case may be, and typical case's time is 10 minutes.
Claims (7)
1, a kind ofly be used to spread, the single step pre-cleaning method of oxidation technology, it is characterized in that cleaning fluid is based on APM solution, its ammoniacal liquor: hydrogen peroxide: the ratio of deionized water volume is 1: 3-5: 15-25, the temperature of solution is 40-80 ℃, the single step scavenging period is 3 to 15 minutes, carry out HF after the prerinse and clean, carry out rinsing and drying then.
2, pre-cleaning method according to claim 1 is characterized in that being added with tetramethyl oxyammonia and complexometric reagent ethylenediamine tetra-acetic acid on APM solution ratio basis.
3, pre-cleaning method according to claim 2 is characterized in that containing in the mixed solution ammoniacal liquor (29%NH
3H
2O), content is 3-5%.
4, pre-cleaning method according to claim 2 is characterized in that containing in the mixed solution TMAH (2.38%), and content is 400-2000ppm.
5, pre-cleaning method according to claim 2 is characterized in that containing in the mixed solution EDTA, and content is 50-200ppm.
6, pre-cleaning method according to claim 2 is characterized in that containing in the mixed solution hydrogen peroxide (30%H
2O
2), content is 10-25%.
7, pre-cleaning method according to claim 2, the content that it is characterized in that DIW in the mixed solution is 85-70%.
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|---|---|---|---|
| CN 03114701 CN1424745A (en) | 2003-01-02 | 2003-01-02 | Single-step clean method for diffuse and oxidation process |
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302096C (en) * | 2003-12-27 | 2007-02-28 | 上海华虹（集团）有限公司 | Pre cleaning solution recipe for deposit side wall medium of flash memory control grid stack structure |
| CN101217102B (en) * | 2007-01-04 | 2010-05-19 | 北京北方微电子基地设备工艺研究中心有限责任公司 | A method to remove surface contaminations on surfaces of semiconductor accessories |
| CN101397499B (en) * | 2008-09-26 | 2011-07-06 | 中国科学院微电子研究所 | TaN material corrosive solution and TaN material corrosion method |
| CN102810461A (en) * | 2011-05-31 | 2012-12-05 | 细美事有限公司 | Substrate processing apparatus and substrate processing method |
| CN103311093A (en) * | 2012-03-12 | 2013-09-18 | 上海凯世通半导体有限公司 | Doping method of PN structure |
| CN107622936A (en) * | 2017-08-23 | 2018-01-23 | 东方环晟光伏（江苏）有限公司 | Method for solar silicon wafers cleaning |
| CN108511316A (en) * | 2017-02-27 | 2018-09-07 | 东莞新科技术研究开发有限公司 | The cleaning method of semiconductor wafer |
| CN116631848A (en) * | 2023-07-20 | 2023-08-22 | 山东有研艾斯半导体材料有限公司 | Silicon wafer cleaning method for improving quality of metal and particles on surface of silicon polished wafer |
-
2003
- 2003-01-02 CN CN 03114701 patent/CN1424745A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302096C (en) * | 2003-12-27 | 2007-02-28 | 上海华虹（集团）有限公司 | Pre cleaning solution recipe for deposit side wall medium of flash memory control grid stack structure |
| CN101217102B (en) * | 2007-01-04 | 2010-05-19 | 北京北方微电子基地设备工艺研究中心有限责任公司 | A method to remove surface contaminations on surfaces of semiconductor accessories |
| CN101397499B (en) * | 2008-09-26 | 2011-07-06 | 中国科学院微电子研究所 | TaN material corrosive solution and TaN material corrosion method |
| CN102810461A (en) * | 2011-05-31 | 2012-12-05 | 细美事有限公司 | Substrate processing apparatus and substrate processing method |
| US9153464B2 (en) | 2011-05-31 | 2015-10-06 | Semes Co., Ltd. | Substrate processing apparatus and substrate processing method |
| CN103311093A (en) * | 2012-03-12 | 2013-09-18 | 上海凯世通半导体有限公司 | Doping method of PN structure |
| CN108511316A (en) * | 2017-02-27 | 2018-09-07 | 东莞新科技术研究开发有限公司 | The cleaning method of semiconductor wafer |
| CN107622936A (en) * | 2017-08-23 | 2018-01-23 | 东方环晟光伏（江苏）有限公司 | Method for solar silicon wafers cleaning |
| CN116631848A (en) * | 2023-07-20 | 2023-08-22 | 山东有研艾斯半导体材料有限公司 | Silicon wafer cleaning method for improving quality of metal and particles on surface of silicon polished wafer |
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Owner name: SHANGHAI HUAHONG (GROUP) CO., LTD.; APPLICANT Free format text: FORMER OWNER: SHANGHAI HUAHONG (GROUP) CO., LTD. Effective date: 20060908 |
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Effective date of registration: 20060908 Address after: 201203 No. 177 blue wave road, Zhangjiang hi tech park, Shanghai, Pudong New Area Applicant after: Shanghai Huahong (Group) Co., Ltd. Co-applicant after: Shanghai integrated circuit research and Development Center Co., Ltd. Address before: 18, Huaihai Road, Shanghai, No. 200020, building 918 Applicant before: Shanghai Huahong (Group) Co., Ltd. |
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