CN1329958C - Cleaning method for semiconductor - Google Patents
Cleaning method for semiconductor Download PDFInfo
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- CN1329958C CN1329958C CNB2003101034492A CN200310103449A CN1329958C CN 1329958 C CN1329958 C CN 1329958C CN B2003101034492 A CNB2003101034492 A CN B2003101034492A CN 200310103449 A CN200310103449 A CN 200310103449A CN 1329958 C CN1329958 C CN 1329958C
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- cleaning
- semiconductor
- water
- silicon oxide
- oxide layer
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Abstract
The present invention relates to a method for cleaning a semiconductor, which is suitable for the use after a dielectric layer between gates of a flash memory is formed. The method comprises the following steps: firstly, a semiconductor wafer is provided; afterwards, a first silicon oxide layer is formed on the semiconductor wafer; sequentially, a floating gate layer is formed on the first silicon oxide layer; then, a second silicon oxide layer is formed on the floating gate layer; subsequently, the first silicon oxide layer, the floating gate layer and the second silicon oxide layer are etched so as to form a gate structure, wherein the second silicon oxide layer is used as the dielectric layer between gates; finally, the semiconductor wafer comprising the gate structure is orderly cleaned by deionized water containing ozone, first cleaning liquid and second cleaning liquid.
Description
Technical field
The invention relates to a kind of cleaning method of Silicon Wafer, and particularly contain the method that the deionized water of ozone comes cleaning wafer relevant for a kind of use.
Background technology
In manufacture of semiconductor, pollutants such as macromolecule, photoresistance or insoluble organic substance may exist and be piled up on the semiconductor crystal wafer, so will be unfavorable for the operation of semiconductor subassembly.The 1st figure is the generalized section that illustrates a semiconductor subassembly, and piles up on this semiconductor subassembly in the processing procedure process pollutant is arranged.
Please refer to the 1st figure, semiconductor subassembly 100 comprises the gate structure (not label) of the semiconductor-based end 102 and a flash memory cell (not illustrating), and this gate structure comprises tunnel oxide 104, float gate 106 and dielectric layer 108.Wherein, the material of the gate 106 of floating comprises polysilicon or silicon nitride, and the material of dielectric layer 108 comprises silica or known to sandwich construction that silicon oxide/silicon nitride/silicon oxide constituted.
In the processing procedure that carries out semiconductor subassembly 100, some pollutants 110 may residue on the sidewall of gate structure of flash memory cell, and these pollutants for example are organic residue or metal ion.Wherein, organic residue may photoresistance carry out etching, coating (Coating) and the process of developing in produce, and metal ion may produce in the process that etching or ion are implanted.
Therefore, in order to obtain to have the quickflashing note body of performance of usefulness preferably (High-Performance) and high-reliability (High-Reliability), thus must be with pollutant removal, that is must clean assembly 100.
A kind ofly developed by the RCA laboratory, and be used for the standard cleaning processing procedure that manufacturing process for cleaning that Silicon Wafer cleans has become industry, this manufacturing process for cleaning is called the RCA manufacturing process for cleaning.A RCA manufacturing process for cleaning comprises and carries out following three main cleaning steps in regular turn:
1. make water (H
2O)/hydrogen peroxide (H
2O
2)/ammoniacal liquor (NH
4OH) mixed liquor (standard cleaning liquid SC1) removes insoluble organic pollution, and wherein the mixed proportion of water, hydrogen peroxide and ammoniacal liquor is 5: 1: 1;
2. make water (H
2O)/and the mixed liquor of hydrofluoric acid (HF) removes thin silicon oxide layer, and wherein can be to being piled up on this silicon oxide layer at the metal pollutant that step 1 produced.In addition, its dilution ratio of water in the mixed liquor and hydrofluoric acid is 50: 1; And
3. make water (H
2O)/hydrogen peroxide (H
2O
2The mixed liquor of)/hydrochloric acid (HCl) (standard cleaning liquid SC2) removes heavy metal atom and heavy-metal pollution thing, and wherein the mixed proportion of water, hydrogen peroxide and hydrochloric acid is 6: 1: 1.
Though the RCA manufacturing process for cleaning is used in the manufacture of semiconductor widely, along with the continuous improvement of manufacture of semiconductor technology, and the appearance of various new materials, this manufacturing process for cleaning no longer can satisfy the demand of various manufacture of semiconductor.For instance, for (for example: flash memory), employed metal material or low-k (Low-K) material uses the cleaning fluid in the RCA manufacturing process for cleaning just may cause etching problem at now semiconductor subassembly.
Summary of the invention
Therefore, purpose of the present invention is exactly that a kind of method for cleaning wafer of novelty is being provided, and to solve in the processing procedure of semiconductor subassembly now, uses problem that known cleaning method suffers from.
The present invention proposes a kind of method for cleaning semiconductor, and after this cleaning method was applicable to that dielectric layer forms between the lock of flash memory, the method comprises provided the semiconductor wafer earlier.Then, on semiconductor crystal wafer, form first silicon oxide layer.Then, on first silicon oxide layer, form the gate layer of floating.Afterwards, on the gate layer of floating, form second silicon oxide layer.Continue it, etching first silicon oxide layer, the float gate layer and second silicon oxide layer, to form gate structure, wherein second silicon oxide layer is as the usefulness of dielectric layer between lock.Then, (De-Ionized DI) cleans the semiconductor crystal wafer that includes gate structure to use the deionized water that contains ozone (Ozonated).Then, comprise that more use first cleaning fluid cleans the wafer that passes through the washed with de-ionized water that contains ozone.Afterwards, use second cleaning fluid to clean the wafer that has cleaned through first cleaning fluid.
The present invention proposes the method that another kind of semiconductor cleans, and after this cleaning method was applicable to that dielectric layer forms between the lock of flash memory, the method comprises provided the semiconductor wafer earlier.Then, on semiconductor crystal wafer, form first silicon oxide layer.Then, on first silicon oxide layer, form the gate layer of floating.Afterwards, on the gate layer of floating, form second silicon oxide layer.Continue it, on second silicon oxide layer, form silicon nitride layer.Then, on silicon nitride layer, form the 3rd silicon oxide layer.Then, etching first silicon oxide layer, the gate layer of floating, second silicon oxide layer, silicon nitride layer and the 3rd silicon oxide layer, to form gate structure, wherein second silicon oxide layer, silicon nitride layer and the 3rd silicon oxide layer are as the usefulness of dielectric layer between lock.Afterwards, use washed with de-ionized water semiconductor crystal wafer ozoniferous.Continue it, use a cleaning fluid to clean semiconductor crystal wafer.Then, use washed with de-ionized water semiconductor crystal wafer ozoniferous.
What deserves to be mentioned is that above-mentioned first cleaning fluid or cleaning fluid for example are to use water (H
2O)/hydrogen peroxide (H
2O
2)/ammoniacal liquor (NH
4OH) mixed liquor, water (H
2O)/hydrogen peroxide (H
2O
2The mixed liquor of the mixed liquor of)/hydrochloric acid (HCl) or hydrofluoric acid (HF)/hydrochloric acid (HCl), or make the mixed liquor of water/hydrogen peroxide/ammoniacal liquor in regular turn, and the mixed liquor of water/hydrogen peroxide/hydrochloric acid.
Other purpose of the present invention and advantage will be suggested in following description, and can be implemented by following embodiment or according to content of the present invention and make that advantage of the present invention and purpose are more plain easily sees.In addition, purpose of the present invention and advantage can be implemented and reached its purpose by claim.
In above-mentioned description and following embodiment is to make it more clear and easy to understand in order to explain spirit of the present invention and content, but the present invention is not limited thereto, and protection scope of the present invention is as the criterion when looking the claim person of defining.
For above and other objects of the present invention, feature and advantage can be become apparent, a preferred embodiment cited below particularly, and cooperate appended graphicly, be described in detail below:
Description of drawings
The 1st figure is the generalized section of a semiconductor subassembly, and piles up on this semiconductor subassembly in the processing procedure process pollutant is arranged.
The 2nd figure is the generalized section of cleaning the semiconductor subassembly of gained through cleaning method of the present invention.
The 3rd figure is the collapse electric charge (Q of MOS structure
BD) measurement of value, and it is for using the comparative result of cleaning method of the present invention and standard cleaning method SC1 and SC2 when carrying out the processing procedure of MOS structure.
The 4th figure is gate coupling efficiency (Gate Coupling Ratios, measurement GCR), and it is for using the comparative result of cleaning method of the present invention and standard cleaning method SC1 and SC2 when carrying out the processing procedure of memory subassembly of memory subassembly.
Description of reference numerals
100,200: semiconductor subassembly
102,202: the semiconductor-based end
104,204: tunnel oxide
106,206: the gate of floating
108,208: dielectric layer
110: pollutant
210: gate structure
212: photoresist layer
Embodiment
Below enumerate preferred embodiment that the present invention is described, in the narration of the icon of embodiment and literal, same or analogous reference number is meant identical or similar part.
The invention provides a kind of method for cleaning wafer of novelty, after this cleaning method is applicable to that dielectric layer forms between the lock of flash memory.The 2nd figure illustrates the generalized section of cleaning the semiconductor subassembly 200 of gained through cleaning method of the present invention.Please refer to the 2nd figure, semiconductor subassembly 200 comprises the semiconductor-based end 202, and is formed with most assemblies (not illustrating) on this semiconductor-based end 202.Then, on the semiconductor-based end 202, form tunnel oxide 204.Then, on tunnel oxide 204, form the gate 206 of floating.Afterwards, on the gate 206 of floating, form dielectric layer 208.Continue it, etching dielectric layer 208, float gate 206 and tunnel oxide 204, to form several gate structures 210, wherein dielectric layer 208 is as the usefulness of dielectric layer between lock.
Wherein, the material at the semiconductor-based end 202 for example is the employed base material of any known technology, and it for example is silicon, germanium or silicon Germanium compound.In addition, the float material of gate 206 for example is polysilicon or silicon nitride.In addition, the material of dielectric layer 208 for example is a silica or by sandwich construction that silicon oxide/silicon nitride/silicon oxide constituted.
On the other hand, when in substrate, forming photoresistance, can be by carrying out micro image etching procedure, and in substrate, form some patterns.Also show such one deck photoresist layer 212 in the 2nd figure, wherein this photoresist layer 212 is formed on the dielectric layer 208.Then, carry out cleaning method of the present invention, to remove the photoresistance residue:
1. (De-Ionized DI) carries out primary cleaning to use the deionized water that contains ozone (Ozonated);
2. use cleaning fluid to carry out cleaning step; And
3. use the deionized water that contains ozone to carry out secondary cleaning,
Wherein, contain ozone deionized water preparation by ozone is imported go dried up in and finish, and ozone concentration for example is between 10 to 80ppm, and preferable working concentration for example is 40ppm.
In first embodiment of the present invention, cleaning fluid is SC1, and it for example is water (H
2O)/hydrogen peroxide (H
2O
2)/ammoniacal liquor (NH
4OH) mixed liquor, and the mixed proportion of water, hydrogen peroxide and ammoniacal liquor is 4～80: 1～5: 1, and preferable mixed proportion for example is 80: 3.1: 2.2.In second embodiment of the present invention, cleaning fluid is SC2, and it for example is water (H
2O)/hydrogen peroxide (H
2O
2The mixed liquor of)/hydrochloric acid (HCl), and the mixed proportion of water, hydrogen peroxide and hydrochloric acid is 4～80: 1～5: 1, and preferable mixed proportion for example is 80: 2.2: 1.3.In the 3rd embodiment of the present invention, cleaning fluid is the mixed liquor (SC1) that makes water/hydrogen peroxide/ammoniacal liquor in regular turn, and the mixed liquor of water/hydrogen peroxide/hydrochloric acid (SC2).Wherein, the mixed proportion of water, hydrogen peroxide and ammoniacal liquor is 4～80: 1～5: 1, and the mixed proportion of water, hydrogen peroxide and hydrochloric acid is 4～80: 1～5: 1, and also preferable mixed proportion SC1 for example is 80: 3.1: 2.2, and SC2 for example is 80: 2.2: 1.3.In the 4th embodiment of the present invention, cleaning fluid is the mixed liquor of hydrofluoric acid (HF)/hydrochloric acid (HCl), and wherein the mixed proportion of hydrofluoric acid, hydrochloric acid and water for example is 1: 1～5: 50～500, and preferable mixed proportion for example is 1: 1.3: 400.
Though be to be that example illustrates the present invention with the photoresistance in the above description, method of the present invention also can be used residual on the wafer to be had in other cleaning as pollutants such as macromolecule, metal ion or other particulates.
In order to measure cleaning performance of the present invention, below be to carry out several tests, its result is shown in the 3rd figure and the 4th figure.The 3rd figure is collapse electric charge (Breakdown the Charge) (Q that illustrates memory cell structure
BD) measurement of value, and it is for using the measurement of cleaning method of the present invention and standard cleaning method SC1 and SC2 gained when carrying out the processing procedure of memory cell structure.Wherein, transverse axis is represented four kinds of different cleaning processes, and the longitudinal axis is represented through after these cleaning processes, the collapse charge Q of the lock oxide layer of the indivedual correspondences that measured
BDValue.These four cleaning processes comprise first embodiment of the present invention and second embodiment, and the standard cleaning method of known use SC1 and SC2, wherein in first embodiment of the present invention, be to use standard cleaning liquid SC1, and in second embodiment of the present invention, be to use standard cleaning liquid SC2.In addition, collapse charge Q
BDThe unit of value is coulomb (Coulomb)/square centimeter (cm
2).By knowing clearly among the 3rd figure, use the collapse charge Q of its lock oxide layer of method of the present invention
BDValue has preferable performance compared to known standard cleaning method.
The 4th figure is the gate coupling efficiency that illustrates memory subassembly (Gate CouplingRatios, measurement GCR), and it is for using the measurement result of cleaning method of the present invention and standard cleaning method SC1 and SC2 gained when carrying out the processing procedure of memory subassembly.By the 4th figure as can be known, the present invention provides a preferable gate coupling efficiency compared to known standard cleaning method.
In addition, also to the memory cell assembly of the cleaning method gained that uses cleaning method of the present invention and known use standard cleaning liquid SC1, carry out yield (Yield) and measure, and compare.On a wafer, can produce 870 crystal grain (Die) altogether, test by specification, only have 682 crystal grain to test on known cleaning method one wafer by specification and use and use method of the present invention to make to have 754 crystal grain on the wafer.In addition, use method of the present invention to carry out the processing procedure of gate structure, on the sidewall of gate structure, can have the less defects number, its per unit (Arbitrary Unit) has 65 defective numbers approximately, and using known cleaning method, the defective number of per unit (Arbitrary Unit) has 682 approximately.
By above-mentioned explanation about embodiments of the invention as can be known, cleaning method of the present invention does not need to prepare employed all cleaning fluids in the known cleaning method, and for example employed dilution ratio is 50: 1 H in RCA cleans
2The O/HF mixed liquor.So the present invention can reduce cost of carry for processing procedure (Cost ofOwnership CoO), and improves yield and reduces the defective number.
Though the present invention discloses as above with preferred embodiment; right its is not in order to limiting the present invention, anyly has the knack of this skill person, without departing from the spirit and scope of the present invention; when can doing a little change and retouching, so protection scope of the present invention is as the criterion when looking the claim person of defining.
Claims (22)
1. after method for cleaning semiconductor, this cleaning method were applicable to that dielectric layer forms between a lock of a flash memory, this cleaning method comprised:
The semiconductor wafer is provided;
On this semiconductor crystal wafer, form one first silicon oxide layer;
On this first silicon oxide layer, form the gate layer of floating;
On floating gate layer, this forms one second silicon oxide layer;
This first silicon oxide layer of etching, this float gate layer and this second silicon oxide layer, to form a gate structure, wherein this second silicon oxide layer is as the usefulness of dielectric layer between this lock;
Use a washed with de-ionized water that contains ozone to include this semiconductor crystal wafer of this gate structure;
Comprise that more using one first cleaning fluid to clean contains this semiconductor crystal wafer of the washed with de-ionized water of ozone through this; And
Use one second cleaning fluid to clean this semiconductor crystal wafer that has cleaned through this first cleaning fluid.
2. method for cleaning semiconductor as claimed in claim 1, wherein the material of this semiconductor crystal wafer comprises silicon.
3. method for cleaning semiconductor as claimed in claim 1, wherein the material of this gate of floating comprises polysilicon.
4. method for cleaning semiconductor as claimed in claim 1, wherein the material of this gate of floating comprises silicon nitride.
5. method for cleaning semiconductor as claimed in claim 1 wherein has been formed with at least one assembly on this semiconductor crystal wafer.
6. method for cleaning semiconductor as claimed in claim 1, wherein at least one fabrication steps formerly, having piled up on this semiconductor crystal wafer has multiple pollutant.
7. method for cleaning semiconductor as claimed in claim 6, wherein those pollutants comprise macromolecule.
8. method for cleaning semiconductor as claimed in claim 7, wherein this macromolecule comprises photoresistance.
9. method for cleaning semiconductor as claimed in claim 1, wherein this first cleaning fluid comprises the mixed liquor of one water/hydrogen peroxide/ammoniacal liquor, and the mixed proportion of water, hydrogen peroxide and ammoniacal liquor is 4～80: 1～5: 1.
10. method for cleaning semiconductor as claimed in claim 1, wherein this first cleaning fluid comprises the mixed liquor of one water/hydrogen peroxide/hydrochloric acid, and the mixed proportion of water, hydrogen peroxide and hydrochloric acid is 4～80: 1～5: 1.
11. method for cleaning semiconductor as claimed in claim 1, wherein this first cleaning fluid comprises the mixed liquor that uses one water/hydrogen peroxide/ammoniacal liquor in regular turn, and the mixed liquor of one water/hydrogen peroxide/hydrochloric acid, wherein the mixed proportion of water, hydrogen peroxide and ammoniacal liquor is 4～80: 1～5: 1, and the mixed proportion of water, hydrogen peroxide and hydrochloric acid is 4～80: 1～5: 1.
12. method for cleaning semiconductor as claimed in claim 1, wherein this first cleaning fluid comprises the mixed liquor of one hydrofluoric acid/hydrochloric acid, and the mixed proportion of hydrofluoric acid, hydrochloric acid and water is 1: 1～5: 50～500.
13. method for cleaning semiconductor as claimed in claim 1, wherein this ozone concentration of deionized water that contains ozone is between 10 to 80ppm.
14. method for cleaning semiconductor as claimed in claim 1, wherein this second cleaning solution comprises that one contains the deionized water of ozone.
15. as 14 described method for cleaning semiconductor of claim the, wherein this ozone concentration of deionized water that contains ozone is between 10 to 80ppm.
16. after a method for cleaning semiconductor, this cleaning method were applicable to that dielectric layer forms between a lock of a flash memory, this cleaning method comprised:
The semiconductor wafer is provided;
On this semiconductor crystal wafer, form one first silicon oxide layer;
On this first silicon oxide layer, form the gate layer of floating;
On floating gate layer, this forms one second silicon oxide layer;
On this second silicon oxide layer, form a silicon nitride layer;
On this silicon nitride layer, form one the 3rd silicon oxide layer;
This first silicon oxide layer of etching, this gate layer of floating, this second silicon oxide layer, this silicon nitride layer and the 3rd silicon oxide layer, to form a gate structure, wherein this second silicon oxide layer, this silicon nitride layer and the 3rd silicon oxide layer are as the usefulness of dielectric layer between this lock;
Use one contains this semiconductor crystal wafer of washed with de-ionized water of ozone;
Use a cleaning fluid to clean this semiconductor crystal wafer; And
Use one contains this semiconductor crystal wafer of washed with de-ionized water of ozone.
17. method for cleaning semiconductor as claimed in claim 16, wherein the material of this gate of floating comprise polysilicon and silicon nitride one of them.
18. method for cleaning semiconductor as claimed in claim 16, wherein this cleaning fluid comprises the mixed liquor of one water/hydrogen peroxide/ammoniacal liquor, and the mixed proportion of water, hydrogen peroxide and ammoniacal liquor is 4～80: 1～5: 1.
19. method for cleaning semiconductor as claimed in claim 16, wherein this cleaning fluid comprises the mixed liquor of one water/hydrogen peroxide/hydrochloric acid, and the mixed proportion of water, hydrogen peroxide and hydrochloric acid is 4～80: 1～5: 1.
20. method for cleaning semiconductor as claimed in claim 16, wherein this cleaning fluid comprises the mixed liquor that uses one water/hydrogen peroxide/ammoniacal liquor in regular turn, and the mixed liquor of one water/hydrogen peroxide/hydrochloric acid, wherein the mixed proportion of water, hydrogen peroxide and ammoniacal liquor is 4～80: 1～5: 1, and the mixed proportion of water, hydrogen peroxide and hydrochloric acid is 4～80: 1～5: 1.
21. method for cleaning semiconductor as claimed in claim 16, wherein this cleaning fluid comprises the mixed liquor of one hydrofluoric acid/hydrochloric acid, and the mixed proportion of hydrofluoric acid, hydrochloric acid and water is 1: 1～5: 50～500.
22. method for cleaning semiconductor as claimed in claim 16, wherein this ozone concentration of deionized water that contains ozone is between 10 to 80ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101034492A CN1329958C (en) | 2003-11-03 | 2003-11-03 | Cleaning method for semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101034492A CN1329958C (en) | 2003-11-03 | 2003-11-03 | Cleaning method for semiconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1614748A CN1614748A (en) | 2005-05-11 |
| CN1329958C true CN1329958C (en) | 2007-08-01 |
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ID=34756673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101034492A Expired - Fee Related CN1329958C (en) | 2003-11-03 | 2003-11-03 | Cleaning method for semiconductor |
Country Status (1)
| Country | Link |
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| CN (1) | CN1329958C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101620982B (en) * | 2008-07-02 | 2011-07-06 | 中芯国际集成电路制造(北京)有限公司 | Method for cleaning wafer and cleaning device |
| CN104103548B (en) * | 2013-04-02 | 2018-02-13 | 中芯国际集成电路制造(上海)有限公司 | Chip pre-cleaning method before active area liner oxidation |
| CN109742013A (en) * | 2018-12-20 | 2019-05-10 | 天津中环领先材料技术有限公司 | A kind of cleaning method reducing silicon chip back side metal |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303482B1 (en) * | 2000-06-19 | 2001-10-16 | United Microelectronics Corp. | Method for cleaning the surface of a semiconductor wafer |
| TW460965B (en) * | 2000-06-28 | 2001-10-21 | Taiwan Semiconductor Mfg | Cleaning method and device for silicon substrate |
| US6399513B1 (en) * | 1999-11-12 | 2002-06-04 | Texas Instruments Incorporated | Ozonated DI water process for organic residue and metal removal processes |
| US6413820B2 (en) * | 1998-10-13 | 2002-07-02 | Advanced Micro Devices, Inc. | Method of forming a composite interpoly gate dielectric |
-
2003
- 2003-11-03 CN CNB2003101034492A patent/CN1329958C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6413820B2 (en) * | 1998-10-13 | 2002-07-02 | Advanced Micro Devices, Inc. | Method of forming a composite interpoly gate dielectric |
| US6399513B1 (en) * | 1999-11-12 | 2002-06-04 | Texas Instruments Incorporated | Ozonated DI water process for organic residue and metal removal processes |
| US6303482B1 (en) * | 2000-06-19 | 2001-10-16 | United Microelectronics Corp. | Method for cleaning the surface of a semiconductor wafer |
| TW460965B (en) * | 2000-06-28 | 2001-10-21 | Taiwan Semiconductor Mfg | Cleaning method and device for silicon substrate |
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| CN1614748A (en) | 2005-05-11 |
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