CN1555088A - Nano two-phase composite structure Zr-Si-N diffusion barrier material and its preparation process - Google Patents
Nano two-phase composite structure Zr-Si-N diffusion barrier material and its preparation process Download PDFInfo
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- CN1555088A CN1555088A CNA2003101189991A CN200310118999A CN1555088A CN 1555088 A CN1555088 A CN 1555088A CN A2003101189991 A CNA2003101189991 A CN A2003101189991A CN 200310118999 A CN200310118999 A CN 200310118999A CN 1555088 A CN1555088 A CN 1555088A
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 48
- 229910007991 Si-N Inorganic materials 0.000 title claims abstract description 36
- 229910006294 Si—N Inorganic materials 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 17
- 230000004888 barrier function Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010409 thin film Substances 0.000 claims abstract 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract 3
- 239000013077 target material Substances 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000427 thin-film deposition Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 3
- 239000010408 film Substances 0.000 abstract description 31
- 239000011159 matrix material Substances 0.000 abstract description 16
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 13
- 230000008021 deposition Effects 0.000 description 13
- 238000004544 sputter deposition Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 7
- 239000003595 mist Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910021419 crystalline silicon Inorganic materials 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 2
- 229910008484 TiSi Inorganic materials 0.000 description 1
- 229910006249 ZrSi Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种纳米双相复合结构Zr－Si－N扩散阻挡层材料及其制备工艺。本发明的材料是由Zr片以及在Zr片上放置若干片尺寸为10mm×10mm×0.7mm的Si片组成的复合靶，在复合靶上沉积有厚度约为90－100nm的Zr－Si－N薄膜。本发明的制备工艺采用射频发应磁控溅射，靶材为Zr片和Si片组成的复合靶，在N2/Ar混合气体中沉积Zr－Si－N薄膜。该薄膜为ZrN和Si4N3组成的双相复合结构，晶界等缺陷密度显著降低,减少了Cu扩散的快速通道，在850℃仍可有效阻挡Cu向Si基体的扩散，是一种性能优良的扩散阻挡层。The invention discloses a Zr-Si-N diffusion barrier layer material with a nanometer two-phase composite structure and a preparation process thereof. The material of the present invention is a composite target composed of a Zr sheet and several Si sheets with a size of 10mm×10mm×0.7mm placed on the Zr sheet, and a Zr-Si-N film with a thickness of about 90-100nm is deposited on the composite target . The preparation process of the invention adopts radio frequency responsive magnetron sputtering, the target material is a compound target composed of Zr sheet and Si sheet, and Zr-Si-N thin film is deposited in N 2 /Ar mixed gas. The film is a two-phase composite structure composed of ZrN and Si 4 N 3 , the density of defects such as grain boundaries is significantly reduced, and the fast channel for Cu diffusion is reduced. It can still effectively block the diffusion of Cu to the Si matrix at 850 ° C. It is a performance Excellent diffusion barrier.
Description
Technical field
The present invention relates to a kind of nano composite material and technology of preparing thereof, especially a kind of nanometer two-phase composite construction Zr-Si-N diffusion barrier material and preparation technology thereof;
Background technology
TiN and TaN are widely studied as the diffusion barrier material of integrated circuit Cu interconnection, and obtain to use, yet owing to need adopt high-temperature process in Cu interconnection manufacture process, TiN and TaN diffusion impervious layer invalid temperature are relatively low, can not finely satisfy the requirement of integrated circuit to the diffusion impervious layer high thermal stability.Deep discovery with research, add the TiN of Si and the compound structure film of TaN and can significantly improve the ability that stops the Cu diffusion as diffusion impervious layer, when TiN and TaN are diffusion impervious layer, its invalid temperature is respectively 550 ℃ and 600 ℃, and the invalid temperature of Ti-Si-N and Ta-Si-N rises to 600 ℃ and 650 ℃ respectively, is attended by TiSi during inefficacy respectively
2And TaSi
2Form mutually.For more than 650 ℃ or can stop the diffusion of Cu under the higher temperature, just need development under this temperature, can stop the new material of Cu diffusion impervious layer, also be research purpose of the present invention.
Summary of the invention
The object of the present invention is to provide a kind ofly can stop the Zr-Si-N diffusion barrier material and the preparation technology thereof of Cu diffusion more than 650 ℃ or under the higher temperature, this Zr-Si-N diffusion barrier material is by ZrN and Si
4N
3The two-phase compound of forming can effectively stop the diffusion of Cu.
Because Zr and Si reaction form ZrSi
2Temperature be 700 ℃, be higher than 650 ℃ of Ta and Ti 550 ℃ respectively, thereby Zr base diffusion impervious layer has more excellent barrier properties.Discover the ZrN diffusion impervious layer 800 ℃ of diffusions that still can effectively stop Cu, adding Si can significantly improve single-phase diffusion barrier material nitride layer and stop the Cu diffusivity, and therefore, the ZrN diffusion impervious layer that adds Si should be a kind of good diffusion barrier material.
Realize that technical scheme of the present invention is: nanometer two-phase composite construction Zr-Si-N diffusion barrier material, by Zr sheet and the last composite target that some Si sheets are formed, the deposition Zr-Si-N film on the Si matrix surface placed thereof; The Zr-Si-N film that is deposited is ZrN and Si
4N
3The two-phase compound of forming.
The preparation technology of this material adopts following steps:
1) choose target: the Si sheet of choosing the Zr sheet and place some lengths of a film * wide * thickness 10mm * 10mm * 0.7mm on the Zr sheet is formed composite target, with the Si sheet as matrix;
2) carry out thin film deposition: with composite target at N
2Use reaction magnetocontrol sputtering in the/Ar mist, deposition generates the Zr-Si-N film that thickness is about 90-100nm; This film is by ZrN and Si
4N
3The two-phase compound of forming; Reaction magnetocontrol sputtering adopts radio-frequency power supply, and matrix is applied the back bias voltage of 0-200V, and sputtering pressure is 0.3Pa, N
2Dividing potential drop is 0.06-0.09Pa.
Adopt the Zr-Si-N film of preparation technology's deposition of the present invention, be ZrN and Si
4N
3The two-phase composite construction of forming, fault of construction such as crystal boundary significantly reduces in the film, has reduced the express passway that Cu spreads therein, has obviously improved the performance that stops the Cu diffusion, 850 ℃ of diffusions that still can effectively stop Cu.
Embodiment
Embodiment 1, is the Si sheet of placing 4 lengths of a film * wide * thickness 10mm * 10mm * 0.7mm on the Zr sheet of Φ 75 * 6mm in diameter * length, is matrix with the single crystalline Si sheet, at N
2With reaction magnetocontrol sputtering deposition Zr-Si-N film, the back of the body rough vacuum of vacuum chamber is 2 * 10 in the/Ar mist
-5Pa adopts radio-frequency power supply, and matrix is applied the back bias voltage of 50V, and sputter gas total gas flow rate is 20sccm, and sputtering pressure is 0.3Pa, N
2Dividing potential drop is 0.06Pa, and the Ar dividing potential drop is 0.24Pa, and sedimentation time is 20min, and the Zr-Si-N film thickness of deposition is 95-100nm.This film is by amorphous ZrN and Si
4N
3The compound of forming, 850 ℃ of annealing after 1 hour Cu diffusion therein still not obvious, can effectively stop the diffusion of Cu.
Embodiment 2, are the Si sheet of placing 4 lengths of a film * wide * thickness 10mm * 10mm * 0.7mm on the Zr sheet of Φ 75 * 6mm in diameter * length, are matrix with the single crystalline Si sheet, at N
2With reaction magnetocontrol sputtering deposition Zr-Si-N film, the back of the body rough vacuum of vacuum chamber is 2 * 10 in the/Ar mist
-5Pa adopts radio-frequency power supply, and matrix is applied the back bias voltage of 100V, and sputter gas total gas flow rate is 20sccm, and sputtering pressure is 0.3Pa, N
2Dividing potential drop is 0.06Pa, and the Ar dividing potential drop is 0.24Pa, and sedimentation time is 20min, and the Zr-Si-N film thickness of deposition is 95-100nm.This film is by nanocrystalline ZrN and amorphous state Si
4N
3The compound of forming, crystal grain diameter is about 6nm, and is still not obvious in 850 ℃ of annealing Cu diffusion therein in 1 hour, has the excellent performance that stops the Cu diffusion.
Embodiment 3, are the Si sheet of placing 4 lengths of a film * wide * thickness 10mm * 10mm * 0.7mm on the Zr sheet of Φ 75 * 6mm in diameter * length, are matrix with the single crystalline Si sheet, at N
2With reaction magnetocontrol sputtering deposition Zr-Si-N film, the back of the body rough vacuum of vacuum chamber is 2 * 10 in the/Ar mist
-5Pa adopts radio-frequency power supply, and matrix is applied the back bias voltage of 200V, and sputter gas total gas flow rate is 20sccm, and sputtering pressure is 0.3Pa, N
2Dividing potential drop is 0.06Pa, and the Ar dividing potential drop is 0.24Pa, and sedimentation time is 20min, and the Zr-Si-N film thickness of deposition is 95-100nm.This film is by nanocrystalline ZrN and amorphous state Si
4N
3The compound of forming, this moment, the ZrN crystal increased mutually, and crystal grain diameter is about 10nm.850 ℃ of annealing after 1 hour Cu diffusion is arranged therein, but the diffusion of Cu still can effectively stop the diffusion of Cu still by diffusion impervious layer.
Embodiment 4, are the Si sheet of placing 4 lengths of a film * wide * thickness 10mm * 10mm * 0.7mm on the Zr sheet of Φ 75 * 6mm in diameter * length, are matrix with the single crystalline Si sheet, at N
2With reaction magnetocontrol sputtering deposition Zr-Si-N film, the back of the body rough vacuum of vacuum chamber is 2 * 10 in the/Ar mist
-5Pa adopts radio-frequency power supply, and matrix is applied the back bias voltage of 200V, and sputter gas total gas flow rate is 20sccm, and sputtering pressure is 0.3Pa, N
2Dividing potential drop is 0.09Pa, and the Ar dividing potential drop is 0.24Pa, and sedimentation time is 20min, and the Zr-Si-N film thickness of deposition is 95-100nm.This film is by nanocrystalline ZrN and crystalline state Si
4N
3The compound of forming, crystal grain diameter is about 20nm.850 ℃ of annealing after 1 hour Cu obvious diffusion is arranged therein, but the diffusion of Cu does not still arrive the Si matrix, still can stop the diffusion of Cu.
Embodiment 5, are the Si sheet of placing 6 lengths of a film * wide * thickness 10mm * 10mm * 0.7mm on the Zr sheet of Φ 75 * 6mm in diameter * length, are matrix with the single crystalline Si sheet, at N
2With reaction magnetocontrol sputtering deposition Zr-Si-N film, the back of the body rough vacuum of vacuum chamber is 2 * 10 in the/Ar mist
-5Pa adopts radio-frequency power supply, and matrix is applied the back bias voltage of 100V, and sputter gas total gas flow rate is 20sccm, and sputtering pressure is 0.3Pa, N
2Dividing potential drop is 0.06Pa, and the Ar dividing potential drop is 0.24Pa, and sedimentation time is 20min, and the Zr-Si-N film thickness of deposition is 95-100nm.This film is by amorphous ZrN and Si
4N
3The compound of forming.850 ℃ annealing 1 hour after Cu do not have obvious diffusion therein, can effectively stop the diffusion of Cu.
Diffusion impervious layers such as Zr-Si-N film of the present invention and existing Ti-Si-N and Ta-Si-N are compared to have: the excellent performance that stops the Cu diffusion; High thermal stability; The Si matrix of at high temperature getting along well reacts and lost efficacy, and is a kind of diffusion impervious layer with application prospect.
Claims (4)
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|---|---|---|---|
| CN 200310118999 CN1284215C (en) | 2003-12-22 | 2003-12-22 | Nano double phase composite structure Zr-Si-N diffusion barrier material and its preparing process |
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|---|---|---|---|
| CN 200310118999 CN1284215C (en) | 2003-12-22 | 2003-12-22 | Nano double phase composite structure Zr-Si-N diffusion barrier material and its preparing process |
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|---|---|
| CN1555088A true CN1555088A (en) | 2004-12-15 |
| CN1284215C CN1284215C (en) | 2006-11-08 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101777469A (en) * | 2010-03-25 | 2010-07-14 | 西安交通大学 | Method for preparing surface conduction electron emission film in W-Si-N nanometer diphase structure |
| CN101775577A (en) * | 2010-03-25 | 2010-07-14 | 西安交通大学 | Method for preparing surface conduction electron emitting film in Zr-Si-N nano double-phase structure |
| CN101921982A (en) * | 2010-09-06 | 2010-12-22 | 厦门大学 | Method for preparing nanostructure nitrogen silicon zirconium coating on the surface of cemented carbide substrate |
| CN102345094A (en) * | 2010-08-04 | 2012-02-08 | 鸿富锦精密工业（深圳）有限公司 | Coating, coated member with coating, and preparation method of coated member |
| CN103253675A (en) * | 2013-06-14 | 2013-08-21 | 兰州理工大学 | Preparation method of superfine ZrSi powder |
-
2003
- 2003-12-22 CN CN 200310118999 patent/CN1284215C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101777469A (en) * | 2010-03-25 | 2010-07-14 | 西安交通大学 | Method for preparing surface conduction electron emission film in W-Si-N nanometer diphase structure |
| CN101775577A (en) * | 2010-03-25 | 2010-07-14 | 西安交通大学 | Method for preparing surface conduction electron emitting film in Zr-Si-N nano double-phase structure |
| CN102345094A (en) * | 2010-08-04 | 2012-02-08 | 鸿富锦精密工业（深圳）有限公司 | Coating, coated member with coating, and preparation method of coated member |
| CN101921982A (en) * | 2010-09-06 | 2010-12-22 | 厦门大学 | Method for preparing nanostructure nitrogen silicon zirconium coating on the surface of cemented carbide substrate |
| CN103253675A (en) * | 2013-06-14 | 2013-08-21 | 兰州理工大学 | Preparation method of superfine ZrSi powder |
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| Publication number | Publication date |
|---|---|
| CN1284215C (en) | 2006-11-08 |
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Assignee: Xian Fulai Electrical Alloy Co., Ltd. Assignor: Xi'an Jiaotong University Contract fulfillment period: 2009.12.1 to 2019.11.30 contract change Contract record no.: 2009610000140 Denomination of invention: Nano double phase composite structure Zr-Si-N diffusion barrier material and preparation process thereof Granted publication date: 20061108 License type: Exclusive license Record date: 2009.12.8 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.12.1 TO 2019.11.30; CHANGE OF CONTRACT Name of requester: XI'AN FULAI ELECTRICAL ALLOY CO., LTD. Effective date: 20091208 |
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