CN1179613C - Surface treatment method to improve adhesive force of organic low dielectric constant layer - Google Patents
Surface treatment method to improve adhesive force of organic low dielectric constant layer Download PDFInfo
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- CN1179613C CN1179613C CNB011331860A CN01133186A CN1179613C CN 1179613 C CN1179613 C CN 1179613C CN B011331860 A CNB011331860 A CN B011331860A CN 01133186 A CN01133186 A CN 01133186A CN 1179613 C CN1179613 C CN 1179613C
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- layer
- adhesion promoter
- dielectric constant
- low dielectric
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Abstract
The present invention provides a surface treatment method for improving the adhesive force of an organic layer with low dielectric constant, which comprises the following steps: firstly, depositing a protection layer on a base plate; then, fast treating the surface of the protection layer by using low radio frequency power plasma containing oxygen in order to form a hydrophilic surface on the surface of the protection layer; subsequently, forming an adhesion accelerant coating layer on the hydrophilic surface; finally, vortically coating an organic layer with low dielectric constant on the adhesion accelerant coating layer, wherein the formation of the hydrophilic surface can change the arrangement of molecules of adhesion accelerant, so hydrophilic group of the molecules of the adhesion accelerant faces to the hydrophilic surface, and hydrophobic group of the molecules of the adhesion accelerant faces to the organic layer with low dielectric constant. Consequently, an interface between the protection layer and the adhesion accelerant coating layer and an interface between the adhesion accelerant coating layer and the organic layer with low dielectric constant are simultaneously improved.
Description
Technical field
The invention provides a kind of surface treatment method that improves adhesive force of organic low dielectric constant layer; in particularly a kind of dielectric layer that can improve between metal connecting line, the method at protective layer-adhesion promoter coating interface and adhesion promoter coating-organic low dielectric constant layer interface.
Background technology
Along with the size of semiconductor element is constantly dwindled and integrated circuit density improves constantly, time relaxation between each plain conductor (RC delay) problem is day by day remarkable to the influence of the operation usefulness of integrated circuit, especially working as technology live width (line width) drops to below 0.25 micron, even during the semiconductor technology below 0.15 micron, the influence that the time relaxation is caused is more obvious.Because the time relaxation between metal interconnecting is the product of the association electric capacity (C) of the resistance value (R) of plain conductor and the dielectric layer between plain conductor, the direction of time relaxation that therefore reduces the metal interconnecting of semiconductor chip has and is to use resistance value lower metal as plain conductor at two: one; The 2nd, the association electric capacity of the dielectric layer between the reduction plain conductor.
At present use aluminium copper (Al:Cu (0.5%)) can't satisfy ultra-large type integrated circuit (ultra largescale integrated circuits gradually as the multi-metal metallization processes (multilevel metallization process) of main material, ULSI circuits) design standard (design rule) be the substitute is with the copper tie line technology (copper interconnect technology) of fine copper as conductor material.Because copper itself has lower resistivity (1.67 μ Ω cm), and can bear higher current density and can not produce electromigration (electro migration) phenomenon of aluminium copper, so copper is at present and the optimal selection of the plain conductor in the following ultra-large type integrated circuit.
In addition, desire reduces the association electric capacity of the dielectric layer between each plain conductor, and present trend is to adopt advanced low-k materials (low k dielectric), and in the advanced low-k materials now, especially the SiLK that is produced with Dow company
TMThe most noticeable, this is because SiLK
TMHave 2.65 low-k (being lower than about 40 percentages of traditional silicon dioxide) and SiLK
TMDo not contain the composition of fluorine (fluorine) in the composition and can not cause pollution metal barrier.In addition, SiLK
TMMore up to 450 ℃, provide a quite wide processing range (process window) to the stability of temperature.Therefore, comprehensively above-mentioned, SiLK
TMWith the integration of process for copper be considerable problem, especially a SiLK
TMInfluence a key factor of metal interconnecting quality especially with the adhesive force of other thin layer such as cover layer (cap layer).
With reference to figure 1; Fig. 1 is the existing method schematic diagram that applies organic low dielectric constant layer; as shown in Figure 1; semiconductor wafer 10 includes a bottom conductive region 11 that is positioned at insulating barrier 12; one is covered in the protective layer 13 on this bottom conductive region 11 and this insulating barrier 12 surfaces; this protective layer 13 is made of silicon nitride or carborundum (SiC); its objective is that another purpose then is intended for etch stop layer in order to prevent that the conduction atom (as copper atom) in the bottom conductive region from spreading outward to dielectric layer.One adhesion promoter layer 14 is located at the surface of this protective layer 13, a SiLK
TMLayer 15 is covered on this adhesion promoter layer 14.And the function of adhesion promoter layer 14 is for strengthening SiLK
TMAdhesive force between layer 15 and the primer (as silicon, silicon dioxide, silicon nitride, aluminium, tantalum, tantalum nitride, titanium nitride etc.).
This adhesion promoter layer (adhesion promoter coating is designated hereinafter simply as APC) 14 refers in particular to the AP4000 type adhesion promoter of being produced by Dow company.(adhesion promoter, AP) molecule generally is dissolved in solvent 1-formaldehyde-propyl acetate AP4000 type adhesion promoter, forms concentration and is lower than 3% solution (being designated hereinafter simply as AP solution).Generally on semiconductor wafer, form SiLK
TMBefore the layer, earlier AP solution is coated on the entire wafer surface, and makes solvent evaporates in the AP solution, the last preparation of finishing this adhesion promoter layer 14 again through one baking procedure by the rotation wafer.
Because the AP molecule is one to have the molecule of a hydrophilic group (hydrophilic group) and a hydrophobic group (hydrophobic group) at least, and SiLK
TMBe essentially the hydrophobic material of the hydrocarbon macromolecule of an aromatic series (aromatic hydrocarbon polymer).In the ideal case, in the time of on APC14 is coated on protective layer 13, the hydrophilic group of AP molecule combines with protective layer 13 and hydrophobic group is exposed to, and SiLK is provided
TM Layer 15 1 good attaching surface.Yet as shown in Figure 2, Fig. 2 is existing APC and protective layer and SiLK
TMStructure enlarged diagram (the intramolecular hydrophilic group of A:AP wherein; The intramolecular hydrophobic group of B:AP; Other element in the C:AP molecule); because protective layer 13 surfaces are not an intact hydrophilic surface (hydrophilic surface); therefore cause the hydrophilic group of AP molecule and hydrophobic group to present irregular arrangement, so the effect of APC14 lowers widely, and then influenced SiLK
TMAdhesive force.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of surface-treated method, to improve the adhesive force of protective layer and adhesion promoter layer and organic low dielectric constant layer and adhesion promoter layer.
In a preferred embodiment of the invention; at first in a substrate, deposit a protective layer; utilize a low radio frequency (radio frequency then; RF) power contains oxygen plasma; an accelerated surface is carried out on this protective layer surface handle, to form a hydrophilic surface (hydrophilic surface) on this protective layer surface.(adbesion promoter coating, APC), last spin coating one organic low dielectric constant layer is on this adhesion promoter layer then to form an adhesion promoter coating on this hydrophilic surface.Wherein the formation of this hydrophilic surface can change the arrangement of this adhesion promoter molecule; the hydrophilic group that makes this adhesion promoter molecule is towards this hydrophilic surface; and the hydrophobic group that makes this adhesion promoter molecule is towards this organic low dielectric constant layer, thereby improves this protective layer and this adhesion promoter coating interface and this adhesion promoter coating and this organic low dielectric constant layer interface simultaneously.
Description of drawings
Fig. 1 is the existing method schematic diagram that applies organic low dielectric constant layer;
Fig. 2 is existing APC, protective layer and SiLK
TMThe structure enlarged diagram of layer (the intramolecular hydrophilic group of A:AP wherein; The intramolecular hydrophobic group of B:AP; Other element in the C:AP molecule); And
Fig. 3 and Fig. 4 are the method schematic diagram that applies organic low dielectric constant layer among the present invention (the intramolecular hydrophilic group of A:AP wherein; The intramolecular hydrophobic group of B:AP; Other element in the C:AP molecule).
Symbol in the accompanying drawing is respectively:
10 semiconductor wafers, 11 bottom conductive regions
12 insulating barriers, 13 protective layers
14 adhesion promoter layers, 15 SiLK
TMLayer
20 semiconductor wafers, 21 bottom conductive regions
22 insulating barriers, 23 protective layers
24 adhesion promoter layers, 25 SiLK
TMLayer
Embodiment
Please refer to Fig. 3 and Fig. 4; Fig. 3 and Fig. 4 are for applying the method schematic diagram of organic low dielectric constant layer among the present invention; as shown in Figure 3; semiconductor wafer 20 includes a bottom conductive region 21 that is positioned at an insulating barrier 22; one utilizes a plasma to strengthen chemical vapour deposition (CVD), and (plasma-enhancedchemical vapor deposition PECVD) is coated on bottom conductive region 21 and insulating barrier 22 lip-deep protective layers 23.As previously mentioned, the major function of protective layer 23 is in order to prevent that the conduction atom (as copper atom) in the bottom conductive region (being generally copper conductor) from migrating to dielectric layer.In a preferred embodiment of the invention, protective layer 23 is made up of silicon nitride, is SiH at a reacting gas that feeds
4And NH
3Novellus Sequal Express PECVD equipment in reaction generate, the silicon nitride thickness of formation is about 350 .In other embodiments of the invention, protective layer 23 also can be made up of carborundum (SiC).
Then, protective layer 23 is carried out an accelerated surface handle, protective layer 23 surfaces are formed have hydroxyl that (hydrophilic surface OH) is in order to combining between follow-up adhesion promoter layer and protective layer 23 surfaces.In a preferred embodiment of the invention, surperficial fast processing is to carry out in a Novellus SequalExpress PECVD equipment, use a low radio frequency (radio frequency, RF) power contain oxygen plasma, preferably use oxygen (O
2) or nitrous oxide (nitrous oxide, N
2O) plasma, RF power bracket are between 100 to 1000 watts, preferably about 200 watts, the gas flow of nitrous oxide is between 2000 to 10000sccm, be preferably about 5000sccm, and the surface treatment temperature is lower than 420 ℃, the processing time is then less than 15 seconds.After the process plasma treatment; utilize a high speed contact angle measuring instrument (high speed contact angle measurement device) to measure the water contact angle (water contact angle) of handling the back silicon nitride surface immediately; measure resulting result and be about 5～10 degree, provable thus plasma-treating technology makes silicon nitride protective layer 23 surfaces form a water-wetted surface really.
Then; as shown in Figure 4; surface deposition one adhesion promoter layer 24 at protective layer 23; depositional mode is for being coated on the entire wafer surface with AP solution earlier; and make solvent evaporates in the AP solution by the rotation wafer, and then finish the preparation of adhesion promoter layer 24 through one baking procedure, the temperature and time of baking is decided on technology; temperature is about between 180 ℃ to 200 ℃, about 60 seconds of stoving time.At last, a SiLK
TMLayer 25 is coated on the adhesion promoter layer 24.
Please refer to Fig. 3 and Fig. 4; as shown in Figure 3; because the surface formation through the protective layer 23 after the plasma treatment has hydroxyl (hydrophilic surface OH); in the time of on adhesion promoter layer 24 is coated on protective layer 23; as shown in Figure 4; the hydrophilic group of AP molecule combines with the hydroxyl on protective layer 23 surfaces and hydrophobic group is exposed last, offers the SiLK of hydrophobicity
TMLayer 25 1 good attaching surface, and then increased protective layer 23 and adhesion promoter layer 24 and adhesion promoter layer 24 and SiLK
TMAdhesive force between the layer 25.
Compare with existing method; the present invention is before deposition adhesion promoter layer 24; earlier protective layer 23 being carried out an accelerated surface handles; make protective layer 23 surfaces form a hydrophilic surface; and then the arrangement of change adhesion promoter molecule; the hydrophilic group that makes the adhesion promoter molecule is not towards hydrophilic surface (being shown among Fig. 3 and Fig. 4); and the hydrophobic group that makes the adhesion promoter molecule is towards organic low dielectric constant layer; thereby improve protective layer-adhesion promoter layer and adhesion promoter layer-organic low dielectric constant layer interface simultaneously, and then reach enhancing protective layer 23 and adhesion promoter layer 24 and adhesion promoter layer 24 and SiLK
TMThe purpose of the adhesive force between the layer 25.
The above only is the preferred embodiments of the present invention, and every equivalence that claim is done according to the present invention changes and modifies, and all should belong to the covering scope of patent of the present invention.
Claims (18)
1. surface treatment method that improves adhesive force of organic low dielectric constant layer, this method includes the following step:
Deposition one is by protective layer that silicon nitride or carborundum constituted in a substrate;
Utilize the oxygen plasma that contains of a low radio frequency power, an accelerated surface is carried out on this protective layer surface handle, to form a hydrophilic surface on this protective layer surface;
Form an adhesion promoter coating on this hydrophilic surface, wherein this adhesion promoter coating is made of an adhesion promoter molecule that has a hydrophilic group and a hydrophobic group at least; And
Spin coating one organic low dielectric constant layer on this adhesion promoter layer;
Wherein the formation of this hydrophilic surface can change the arrangement of this adhesion promoter molecule; the hydrophilic group that makes this adhesion promoter molecule is towards this hydrophilic surface; and the hydrophobic group that makes this adhesion promoter molecule is towards this organic low dielectric constant layer, thereby improves this protective layer and this adhesion promoter coating interface and this adhesion promoter coating and this organic low dielectric constant layer interface simultaneously.
2. the method for claim 1, wherein this protective layer is formed by plasma fortified chemical vapour deposition technique.
3. the method for claim 1, wherein the employed oxygen plasma that contains of this surface treatment is the nitrous oxide plasma.
4. method as claimed in claim 3, wherein, this N
2The O gas flow is 2000 to 10000sccm.
5. the method for claim 1, wherein this contains the employed RF power bracket of oxygen plasma between 100 to 1000 watts.
6. the method for claim 1, wherein this RF power is about 200 watts.
The method of claim 1, wherein this surface-treated time less than 15 seconds.
8. the method for claim 1, wherein this surface-treated temperature is lower than 420 ℃.
9. the method for claim 1, wherein AP4000 adhesion promoter that provided for Dow company of this adhesion promoter coating.
10. the method for claim 1, wherein SiLK that provided for Dow company of this organic low dielectric constant layer
TM
11. a surface treatment method that is used for semiconductor technology, this method comprises:
Deposition one inorganic silicon-containing layer in a substrate;
An accelerated surface is carried out on this protective layer surface handle, utilize one to contain oxygen plasma, form a hydrophilic surface on this protective layer surface;
On this hydrophilic surface, form an adhesion promoter coating; And
Spin coating one organic low dielectric constant layer on this adhesion promoter layer.
12. method as claimed in claim 11, wherein, this inorganic silicon-containing layer is made of silicon nitride or carborundum.
13. method as claimed in claim 11, wherein, this inorganic silicon-containing layer is formed by plasma fortified chemical vapour deposition technique.
14. method as claimed in claim 11, wherein, the employed oxygen plasma that contains of this surface treatment is the nitrous oxide plasma.
15. method as claimed in claim 14, wherein, this N
2The O gas flow is about 5000sccm.
16. method as claimed in claim 11, wherein, this surface-treated time was less than 15 seconds.
17. method as claimed in claim 11, wherein, the AP4000 adhesion promoter that this adhesion promoter coating is provided for Dow company.
18. method as claimed in claim 11, wherein, the SiLK that this organic low dielectric constant layer is provided for Dow company
TM
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011331860A CN1179613C (en) | 2001-09-20 | 2001-09-20 | Surface treatment method to improve adhesive force of organic low dielectric constant layer |
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| CNB011331860A CN1179613C (en) | 2001-09-20 | 2001-09-20 | Surface treatment method to improve adhesive force of organic low dielectric constant layer |
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| CN1406107A CN1406107A (en) | 2003-03-26 |
| CN1179613C true CN1179613C (en) | 2004-12-08 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1839468B (en) * | 2003-10-08 | 2010-11-24 | 霍尼韦尔国际公司 | Repairing damage to low-K dielectric materials using silylating agents |
| US6902440B2 (en) * | 2003-10-21 | 2005-06-07 | Freescale Semiconductor, Inc. | Method of forming a low K dielectric in a semiconductor manufacturing process |
| JP4422671B2 (en) | 2005-12-06 | 2010-02-24 | トヨタ自動車株式会社 | Semiconductor device and manufacturing method thereof |
| US20080067502A1 (en) * | 2006-09-14 | 2008-03-20 | Nirupama Chakrapani | Electronic packages with fine particle wetting and non-wetting zones |
| US20090056991A1 (en) * | 2007-08-31 | 2009-03-05 | Kuhr Werner G | Methods of Treating a Surface to Promote Binding of Molecule(s) of Interest, Coatings and Devices Formed Therefrom |
| CN102543697B (en) * | 2010-12-22 | 2014-02-26 | 中芯国际集成电路制造(上海)有限公司 | Method for manufacturing tunnel oxide layer window in electrically erasable programmable read only memory (EEPROM) |
| CN102354670B (en) * | 2011-10-13 | 2013-08-07 | 无锡世一电力机械设备有限公司 | Comprehensive surface processing method for improving capsulation reliability of semiconductor |
| CN105206617B (en) * | 2015-08-26 | 2018-09-18 | 武汉华星光电技术有限公司 | The manufacturing method of array substrate |
| CN112397460B (en) * | 2019-08-16 | 2023-04-28 | 矽磐微电子(重庆)有限公司 | Multi-die package structure, chip package structure and respective manufacturing methods |
| CN111465217A (en) * | 2020-03-10 | 2020-07-28 | 深圳市信维通信股份有限公司 | Manufacturing method of high-frequency flexible substrate for 5G communication |
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Granted publication date: 20041208 |