CN102386128A - Method for modifying SiCOH film microstructure - Google Patents
Method for modifying SiCOH film microstructure Download PDFInfo
- Publication number
- CN102386128A CN102386128A CN2011102082553A CN201110208255A CN102386128A CN 102386128 A CN102386128 A CN 102386128A CN 2011102082553 A CN2011102082553 A CN 2011102082553A CN 201110208255 A CN201110208255 A CN 201110208255A CN 102386128 A CN102386128 A CN 102386128A
- Authority
- CN
- China
- Prior art keywords
- film
- sicoh film
- sicoh
- microstructure
- modification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Formation Of Insulating Films (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
The invention belongs to the technical field of manufacturing of semiconductor integrated circuits and particularly relates to a method for modifying a SiCOH film microstructure. In the invention, a SiCOH film can be firstly prepared by a sol-gel method and a spin coating technology, then is subjected to annealing treatment and finally placed under a wide-spectrum ultraviolet lamp for irradiation, thus the modification of the SiCOH film microstructure can be realized and a crosslinked bonding structure in the film can be added. The method provided by the invention can be used for obviously improving the mechanical property of the SiCOH film.
Description
Technical field
The invention belongs to semiconductor integrated circuit manufacturing technology field, be specifically related to a kind of method of the SiCOH of modification film microstructure.
Background technology
In the very lagre scale integrated circuit (VLSIC) interconnection system, low-k (
k) the alternative traditional SiO of material
2Medium becomes the main flow that the Cu connected medium is studied.Therefore the SiCOH film of report has very low owing to contain organic carbon group and nanoaperture at present
kValue (
k=2.3-3.0), become the low of broad research
kOne of material [1-2].Lower in order to obtain further
k(
k<2.3) the SiCOH film, just need in this film, introduce more organic carbon group and more hole [3].Yet this causes other performance of this film to be degenerated again conversely, makes the SiCOH film on technology is integrated, be faced with very big challenge, especially in the CMP process process, occurs low
kThe peeling off or subside of film.
As everyone knows, the chemical bonding between each element of the structures shape of material its performance, especially material internal.Become bond structure, the material that is expected to obtain to have specific function through forming specific chemical bond and space.SiCOH film with regard to the sol-gel process preparation; Si-C, Si-O, C-H, O-H key are contained in its inside; Both exist with alkyl and OH-form wherein; Be equivalent in material, introduce the structure of open chain, cause the compactness of film not high, also can have influence on mechanical properties in films [4] simultaneously.If after film forms, through external means make in the SiCOH film between the alkyl and alkyl and hydroxyl between new linking takes place, so just can form the crosslinked chemical bonding structure of more space, so be expected to improve the performance of SiCOH film.According to the document of domestic and international public reported, the method that material film is modified mainly is a plasma surface treatment, comprises nitrogen gas plasma, oxygen gas plasma, also has number of C F
nPlasma surface treatment.Yet this method produces ionic charge and trap at film surface easily, causes its leakage current to increase.In addition, it also can introduce exogenous impurity in film, for example, adopts nitrogen plasma treatment can introduce the nitrogen element.In addition, the action effect of this method is more limited, is confined to usually modify in several nano thickness scopes of film surface.
List of references:
[1].?Hatton?B?D,?Landsdron?K,?Hunks?W?J.?[J]?Materials?Today,?2006,?(9):24-30.
[2].?Louveaa?O,?Louis?D,?Assous?M.?[J]?Microelectron.Eng,?2002,?61/62?:867.
[3].?ITRS?roadmap?(2004)
[4].?Fu?S,?Qian?K?J,?Ding?S?J,?et?al.?2010?10th?International?Conference?on?Solid-State?and?Integrated?Circuit?Technology?Proceedings,?2010,?CFP10829-PRT:1033-1035。
Summary of the invention
The objective of the invention is to propose a kind of method of micro-structural of simple to operate, little, the modification SiCOH film that can significantly improve thin film mechanical performance to the dielectric constant influence of film.
The method of the micro-structural of the modification SiCOH film that the present invention proposes; Be through the SiCOH film being carried out the ultraviolet irradiation of different time, different wave length; Realization makes crosslinked C-C and C-O key relative amount increase, thereby improves its mechanical property the modification of chemical bonding in the SiCOH film.
The method of the modification SiCOH film microstructure that the present invention proposes, concrete steps are:
(1) at first, with MTES and 1,2-two (triethoxy is silica-based) ethane is precursor, prepares the SiCOH film through sol-gel process and spin coating technique;
(2) then, this SiCOH film is carried out thermal anneal process;
(3) last, the SiCOH film is carried out wide general ultra violet lamp, to modify the micro-structural of film.
Among the present invention, the used precursor sol solution of step (1) preparation SiCOH film is by MTES, 1,2-two (triethoxy is silica-based) ethane, surfactant P
123, hydrochloric acid, ethanol and deionized water form.The preparation condition of this sol solution was: 40 ℃ ~ 100 ℃ stirred in water bath 1 ~ 5 hour.
Among the present invention, the described thermal anneal process of step (2) is that spin coating gained film is at first placed in the baking oven, and slaking is 24 ~ 100 hours under 50 ℃ ~ 200 ℃ temperature; Place annealing furnace then, feed nitrogen or rare gas, slowly rise to 150 ~ 350 ℃ by room temperature, and kept 1 ~ 5 hour, slowly reduce to room temperature then.
Among the present invention, the described general ultra violet lamp of step (3), used ultraviolet wavelength is 200 ~ 400 nanometers; The temperature of film is a room temperature during irradiation; The residing environment of film is an atmospheric atmosphere, also can be nitrogen or argon atmosphere; Vertical range between ultraviolet lamp tube and the SiCOH film is 10～20 centimetres; Exposure time is 5 ~ 50 hours.
Among the present invention, the modification of described film microstructure shows as C-C linkage content increase in the film, and the content of C-Si key reduces, and has introduced new C-O key simultaneously, thereby the SiCOH mechanical properties in films is obviously improved.The improvement of so-called thin film mechanical performance is embodied in the increase of the hardness and the Young's modulus of film.
The present invention proposes to adopt the method for ultraviolet light irradiation to modify the micro-structural in the SiCOH film; Not only simple to operate; In normal temperature and atmospheric environment, just can carry out; And changed the content of different chemical Cheng Jian in the film effectively, less to the influence of the dielectric constant of film, but significantly improved mechanical properties in films.
Embodiment
Be an embodiment who adopts the modification SiCOH film microstructure of the present invention's proposition below.Implementation step is following:
1) a low-resistance monocrystalline silicon (100) substrate, the column criterion of going forward side by side cleaning are provided.
2) the precursor sol solution is by MTES, 1,2-two (triethoxy is silica-based) ethane, surfactant P
123, hydrochloric acid, ethanol and deionized water form.With MTES, 1,2-two (triethoxy is silica-based) ethane mixes and stirs until mixing, and wherein MTES is 0.356 gram, and 1,2-two (triethoxy is silica-based) ethane is 1.037 grams.Then with surfactant P
123, hydrochloric acid, ethanol and deionized water the mixture back that stirs slowly add in the mixed liquor of above-mentioned precursor surfactant P wherein
123Be 0.556 gram, hydrochloric acid is 2.813 grams, and ethanol is 4.987 grams, in 60 ℃ water-bath, continues to stir 2 hours, processes sol solution, is cooled to room temperature.
3) above-mentioned sol solution at room temperature is spin-coated on the low-resistance monocrystalline silicon piece that standardization is cleaned.
4) film of spin coating gained is at first placed in the baking oven 60 ℃ environment matured 70 hours, placed annealing furnace then, feed nitrogen, slowly rise to 350 ℃ by room temperature, and kept 3 hours, slowly reduce to room temperature then.
5) will put into irradiation under the wide general uviol lamp by the film that step 4 obtains, to modify the micro-structural of film.The used wavelength of wherein general ultra violet lamp is 200 ~ 400 nanometers, and the film sample temperature is a room temperature, and the irradiation environment is an atmospheric atmosphere, and the vertical range between ultraviolet lamp tube and the SiCOH film is 15 centimetres, and exposure time is 6 hours.
The dielectric constant of film is measured through the capacitance-voltage (C-V) of metal-inter-level dielectric-semiconductor (MIS) structure and is obtained.Film is formed and the chemical bonding state is confirmed through the analysis of x-ray photoelectron power spectrum.Mechanical properties in films obtains by dynamic nanometer mechanics tester.
Chemical bonding structure and the relatively comparison of percentage composition thereof of table 1 for existing in the SiCOH film before and after the ultraviolet irradiation.For the SiCOH film that does not experience ultraviolet irradiation, there are C-Si and C-C key in this film, their relative percentage composition is 91% and 9%.When ultraviolet irradiation after 6 hours, new C-O key has appearred in the film, and its relative amount reaches 4%, and the relative amount of C-C key increases, and the relative amount of C-Si key reduces.In addition, ultraviolet irradiation is after 6 hours, and the dielectric constant of measured SiCOH film also increases a little.This shows that ultraviolet irradiation modified the chemical bonding state in the SiCOH film effectively, make that C-H in the film, H-O key rupture after, again C-C takes place and C-O is crosslinked, film compactness improves.
Chemical bonding structure and the comparison of percentage composition relatively thereof in the SiCOH film before and after table 1 ultraviolet irradiation
| The ultraviolet irradiation time | C-Si key percentage composition | C-C key percentage composition | C-O key percentage composition | Dielectric constant |
| 0 hour | 91% | 9% | 0 | ~2.0 |
| 6 hours | 84% | 12% | 4% | ~2.2 |
Table 2 is the one-tenth key characteristic of silicon atom in the SiCOH film before and after the ultraviolet irradiation and the comparison of percentage composition relatively thereof, and wherein M represents and has 2 OH groups on the Si atom, and D represents and has 1 OH group on the Si atom, and on behalf of the Si atom, T do not have the OH group.Through relatively can finding, the SiCOH film through 6 hours ultraviolet irradiation after, M structure relative amount remains unchanged in the film, but the content of T structure reduces relatively, D content increases relatively.This has proved that further ultraviolet irradiation has changed the one-tenth bonded state of silicon atom effectively.
The one-tenth key characteristic of silicon atom and the comparison of percentage composition relatively thereof in the SiCOH film before and after table 2 ultraviolet irradiation
| The ultraviolet irradiation time | The M percentage composition | The D percentage composition | The T percentage composition |
| 0 hour | 14% | 56% | 30% |
| 6 hours | 14% | 68% | 18% |
Table 3 is for being standard with 50% cumulative probability, the SiCOH film before and after the ultraviolet irradiation amount to modulus (E
r) and the comparison of hardness (H).The E of the SiCOH film of handling without ultraviolet
rBe about 3.8GPa and 0.3GPa respectively with H.Along with the ultraviolet irradiation time is increased to 6 hours, the E of this film
rBe increased to 7.4GPa and 1.0GPa respectively with H.This shows that ultraviolet irradiation has improved mechanical properties in films effectively.
SiCOH film before and after table 3 ultraviolet irradiation amount to modulus (E
r) and the comparison of hardness (H)
| The ultraviolet irradiation time | Amount to modulus (E r） | Hardness (H) |
| 0 hour | 3.8GPa | 0.3GPa |
| 6 hours | 7.4GPa | 1.0GPa |
Claims (4)
1. method of modifying the SiCOH film microstructure is characterized in that concrete steps are:
(1) at first, with MTES and 1,2-two (triethoxy is silica-based) ethane is precursor, prepares the SiCOH film through sol-gel process and spin coating technique;
(2) then, this SiCOH film is carried out thermal anneal process;
(3) last, the SiCOH film is carried out wide general ultra violet lamp, to modify the micro-structural of film.
2. the method for modification according to claim 1 SiCOH film microstructure is characterized in that, the sol solution of preparation SiCOH film is by MTES, 1,2-two (triethoxy is silica-based) ethane, surfactant P
123, hydrochloric acid, ethanol and deionized water form; The preparation condition of this sol solution was: 40 ℃ ~ 100 ℃ stirred in water bath 1 ~ 5 hour.
3. the method for modification SiCOH film microstructure according to claim 1 is characterized in that, the described thermal anneal process of step (2) is that spin coating gained film is placed in the baking oven earlier, and slaking is 24 ~ 100 hours under 50 ℃ ~ 200 ℃ environment; Place annealing furnace then, feed nitrogen or rare gas, rise to 150 ~ 350 ℃ by room temperature, and kept 1 ~ 5 hour, reduce to room temperature then.
4. the method for modification SiCOH film microstructure according to claim 1 is characterized in that, the described general ultra violet lamp of step (3), and used ultraviolet wavelength is 200 ~ 400 nanometers; The temperature of film is a room temperature during irradiation; The residing environment of film is atmospheric atmosphere, nitrogen atmosphere or argon atmosphere; Vertical range between ultraviolet lamp tube and the SiCOH film is 10～20 centimetres; Exposure time is 5 ~ 50 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102082553A CN102386128A (en) | 2011-07-25 | 2011-07-25 | Method for modifying SiCOH film microstructure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102082553A CN102386128A (en) | 2011-07-25 | 2011-07-25 | Method for modifying SiCOH film microstructure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102386128A true CN102386128A (en) | 2012-03-21 |
Family
ID=45825408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102082553A Pending CN102386128A (en) | 2011-07-25 | 2011-07-25 | Method for modifying SiCOH film microstructure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102386128A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683275A (en) * | 2012-06-08 | 2012-09-19 | 复旦大学 | Super-low dielectric constant (k) material thin film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050194619A1 (en) * | 2005-01-21 | 2005-09-08 | International Business Machines Corporation | SiCOH dielectric material with improved toughness and improved Si-C bonding, semiconductor device containing the same, and method to make the same |
| CN1852772A (en) * | 2003-07-21 | 2006-10-25 | 艾克塞利斯技术公司 | Ultaviolet curing processes for advanced low-k materials |
| CN101533774A (en) * | 2008-03-14 | 2009-09-16 | 章蕾 | Method for enhancing mechanical strength of SiCOH film with low dielectric constant |
| CN101789418A (en) * | 2010-03-11 | 2010-07-28 | 复旦大学 | Porous ultra-low dielectric constant material film and preparation method thereof |
-
2011
- 2011-07-25 CN CN2011102082553A patent/CN102386128A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1852772A (en) * | 2003-07-21 | 2006-10-25 | 艾克塞利斯技术公司 | Ultaviolet curing processes for advanced low-k materials |
| US20050194619A1 (en) * | 2005-01-21 | 2005-09-08 | International Business Machines Corporation | SiCOH dielectric material with improved toughness and improved Si-C bonding, semiconductor device containing the same, and method to make the same |
| CN101533774A (en) * | 2008-03-14 | 2009-09-16 | 章蕾 | Method for enhancing mechanical strength of SiCOH film with low dielectric constant |
| CN101789418A (en) * | 2010-03-11 | 2010-07-28 | 复旦大学 | Porous ultra-low dielectric constant material film and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683275A (en) * | 2012-06-08 | 2012-09-19 | 复旦大学 | Super-low dielectric constant (k) material thin film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI304077B (en) | Method of forming organic silica-based film | |
| TWI316524B (en) | ||
| TWI585127B (en) | Composition for forming silica based insulating layer and method for manufacturing the same, silica based insulating layer and method for manufacturing the same | |
| US7648894B2 (en) | Coating composition for insulating film production, preparation method of insulation film by using the same, insulation film for semi-conductor device prepared therefrom, and semi-conductor device comprising the same | |
| TWI284140B (en) | Method for forming porous silica film | |
| EP1858996B8 (en) | Coating composition for dielectric insulating film, dielectric insulating film prepared therefrom, and electric or electronic device comprising the same | |
| TWI356830B (en) | ||
| US8932702B2 (en) | Low k dielectric | |
| US7497965B2 (en) | Insulating film-forming composition, insulating film and production method thereof | |
| TWI326891B (en) | Material for forming adhesion reinforcing layer, adhesion reinforcing layer, semiconductor device, and manufacturing method thereof | |
| TWI314936B (en) | ||
| JP2006229201A (en) | Low dielectric material and method for manufacturing same | |
| TW200808907A (en) | Composition for forming insulating films, process for production thereof, silica-base insulating films, and process for the formation of the films | |
| TWI328600B (en) | Composition for forming porous film, porous film and method for forming the same, interlevel insulator film and semiconductor device | |
| CN102386128A (en) | Method for modifying SiCOH film microstructure | |
| CN102683275A (en) | Super-low dielectric constant (k) material thin film and preparation method thereof | |
| KR20080042689A (en) | Composition for forming coating and coating formed of compostion | |
| US20080248328A1 (en) | Process for Preparing a Zeolite-Containing Film | |
| JP2000340651A (en) | Manufacture of film having low dielectric constant | |
| US20080026590A1 (en) | Metal organic deposition precursor solution synthesis and terbium-doped SiO2 thin film deposition | |
| JP2005139265A (en) | Coating liquid for forming silica-based film | |
| JPH06181201A (en) | Insulating film for semiconductor device and liquid applied for growing that insulating film | |
| JP6042151B2 (en) | Insulating material for semiconductor containing silica particles | |
| US20040126595A1 (en) | Nanopore forming material for forming insulating film for semiconductors and low dielectric insulating film comprising the same | |
| JP2011006539A (en) | Coating silica-based film forming composition, silica-based film using the same, and semiconductor device using the film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120321 |