• 沒有找到結果。

本實驗中,我們可在 2×10-3 torr 的濺鍍壓力、射頻功率 200W 和 氬氣流量 9.5 sccm、氮氣流量 0.5 sccm 下,在砷化鎵基板上成長出非 晶質的鉭基氮化物,並可歸納以下一些結論:

1. 鉭基氮化物擴散阻礙層存在銅金屬和砷化鎵基板間,的確可以避免 銅鎵或銅砷化合物的介面相產生。

2. 非晶質的鉭基氮化物可經由 600℃左右的熱處理退火後,產生如

(100)、(002)、(101)、(102)等結構面的多晶 Ta2N。

3. 鉭基氮化物在銅膜和砷化鎵基板間,進行真空氣氛、溫度 575℃下 之退火一小時,可以壓抑銅金屬和砷化鎵間之擴散行為,而在 600

℃以上的溫度,則發現鉭砷、銅鎵等化合物。

4. 在雜質源砷或鎵氣氛下進行熱處理,並不能有效提升耐熱溫度和壓 抑銅金屬和砷化鎵間之擴散問題。

5. 鉭基氮化物的電阻率約為280~330μΩ-cm

參考文獻

1. R. E. Williams, Gallium Arsenide Processing Techniques, 學風科學 圖書出版社, p.17-51, 1984.

2. M. Passlack, M. Hong, J. P. Kwo, L.W. Tu, “Recombination velocity at oxide-GaAs interfaces fabricated by in situ molecular beam epitaxy,” Applied Physics Letters, Vol. 68, p.3605-3607, 1996.

3. 莊達人, VLSI 製造技術, 高立圖書出版社, p.146-181, 1998.

4. Alexander E. Braun, “Aluminum Persists as Copper Age Dawns,”

Semiconductor International, p.58-66, 1999.

5. 顧子琨, “極大型積體電路之銅連結線技術,” 電子月刊第五卷第六 期, p.117-133, 1999.

6. Y. Igarashi, T. Yamanobe, T. Ito, “Thermal stability of copper interconnects fabricated by dry-etching process,” Thin Solid films, 262, p.124-128, 1995.

7. S. Wolf, Silicon processing for the VLSI Era– Volume Ⅱ, Lattice Press. , p.84-175, 1990.

8. H. Ono, T. Nakano, T. Ohta, “Diffusion barrier effects of transition metals for Cu/M/Si multilayers (M = Cr, Ti, Nb, Mo, Ta, W),”

Applied Physics Letters, 64, p.1511-1513, 1994.

9. J. Chuang, S. Tu, M. Chen, “Sputter-deposited Mo and reactively sputter-deposited Mo-N films as barrier layers against Cu diffusio n,”

Thin Solid Films, 346, p.299-306, 1999.

10. J. O. Olowolage, J. Li, J. W. Mayer, “Effects of oxygen in TiN x on the diffusion of Cu in Cu/TiN/Al and Cu/TiNx/Si structures,” Applied Physics Letters, 58, p.469-471, 1991.

11. S. Q. Wang, S. Suthar, C. Hoeflich, B. J. Burrow, “Reactively sputtered TiN as a diffusion barrier between Cu and Si,” J. Appl.

Phys., 68, p.5176-5183, 1990.

12. S. Q. Wang, S. Suthar, C. Hoeflich, B. J. Burrow, “Diffusion barrier properties of TiW between Si and Cu,” J. Appl. Phys., 73, p.2301-2306, 1993.

13. E. Kolawa, J. S. Chen, J. S. Reid, P, J. Pokelan, M.A. Nicolet,

“Tantalum-based diffusion barriers in Si/Cu VLSI metallizations,” J.

Appl. Phys., 70, p.1369, 1991.

14. R. Hoogeveen, M. Moske, H. Geisler, K. Samwer, “Texture and phase transformation of sputter-deposited metastable Ta films and Ta/Cu multilayers,” Thin Solid Films 275, p.203-206, 1996.

15. M. Stavrev, D. Fischer, C. Wenzel, K. Drescher, N. Mattern,

“Crystallographic and morphological characterization of reactively sputtered Ta, Ta-N and Ta-N-O thin films,” Thin Solid Films, 307, p.79-88, 1997.

16. T. Oku, E. Kawakami, M. Uekubo, K. Takahiro, S. Yamaguchi, M.

Murakami, “Diffusion barrier property of TaN between Si and Cu,”

Appl. Surf. Sci., 99, p.265-272, 1996.

17. K. Min, K. Chun, K. Kim, “Comparative study of tantalum and tantalum nitrides (Ta2N and TaN) as a diffusion barrier for Cu metallization,” J. Vac. Sci. Technol. B, Vol. 14, No. 5, p.3263-3269, 1996.

18. M. Stavrev, C. Wenzel, A. Moller, K. Drescher, “Sputtering of tantalum-based diffusion barriers in Si/Cu metallization: effects of gas pressure and composition,” Applied Surface Science, 91, p.257-262, 1995.

19. J. Chuang, M. Chen, “Properties of thin Ta-N films reactively sputtered on Cu/SiO2/Si substrates,” Thin Solid Films, 322, p.213-217, 1998.

20. M. Takeyama, A. Noya, T. Sase, A. Ohta, “Properties of TaNx films as diffusion barriers in the thermally stable Cu/Si contact systems,” J.

Vac. Sci. Technol. B, 14, p.674-678, 1996.

21. K. Wakasugi, M. Tokunaga, T. Sumita, H. Kubota, M. Nagata, Y.

Honda, “Superconductivity of reactively sputtered TaN film for ULSI process,” Physica B, 239, p.29-31, 1997.

22. X. Sun, E. Kolawa, J. Chen, J. S. Reid, M. A. Nicolet, “Properties of reactively sputter-deposited Ta-N thin films,” Thin Solid Films, 236, p.347-351, 1993.

23. M. Stavrev, D. Fischer, A. Preub, C. Wenzel, N. Mattern, “Study of nanocrystalline Ta(N,O) diffusion barriers for use in Cu metallization,” Microelectronic Engineering, 33, p.269-275, 1997.

24. M. H. Tsai, S. C. Sun, C. P. Lee, H. T. Chiu, C. E. Tsai, S. J. Chuang, S. C. Wu, “Metal-organic chemical vapor deposition of tantalum nitride barrier layers for ULSI applications,” Thin Solid Films, 270, p.531-536, 1996.

25. C. Lee, Y. Shin, “Ta-Si-N as a diffusion barrier between Cu and Si,”

Materials chemistry and Physics, Vol. 57, p.17-22, 1998.

26. Y. Lee, B. Suh, M. S. Kwon, C. Park, “Barrier properties and failure mechanism of Ta-Si-N thin films for Cu interconnection,” J. Appl.

Phys., Vol. 85, No. 3, p.1927-1934, 1999.

27. Y. Lee, B. Suh, S. Rha, C. Park, “Structural and chemical stability of Ta-Si-N thin film between Si and Cu,” Thin Solid Films, 320, p.141-146, 1998.

28. C. Y. Chang, F. Kai, GaAs High-Speed devices, John Wiley & Sons Inc., Chap. 2, 1994.

29. N. Terao, “Structure of Tantalum Nitrides,” Japan J. Appl. Phys., 10, p.248-259, 1971.

30. 許振聲、陳錦山, “ 鉭基氮化物擴散阻礙層在銅金屬化系統之失效

機制,” 真空科技卷12, p.5-17, 1999.

31. C.Y. Chang, Francis Kai, GaAs High-Speed Devices, John Wiley &

Sons Inc., p.288-294, 1994.

32. K. Kim, M. Kniffin, R. Sinclair, C. R. Helms, “Interfacial reactions in the Ti/GaAs system,” J. Vac. Sci. Technol. A, Vol. 6, No. 3, p.1473-1477, 1988.

33. M. Cuziewicz, A. Piotrowska, E. Kaminska, K. Golaszewska, A.

Turos, E. Mizera, A. Winiarski, J. Szade, “Characteristics of sputter-deposited TiN, ZrB2 and W2B diffusion barriers for advanced metallizations to GaAs,” Solid-State Electronics, 43, p.1055-1061, 1999.

34. T. Feng, A. Dimoulas, A. Christou, G. Constantinidis, Z. Hatzopoulos,

“Failure mechanisms of GaAs MESFETs with Cu/Refractory Metallized Gates,” Microelectron. Reliab., Vol. 37, p.1699-1702, 1997.

35. G. Scherb, D. M. Kolb, “Cu deposition onto n-GaAs (100): optical and current transient studies,” Journal of Electroanalytical Chemistry, 396, p.151-159, 1995.

36. R. Beyers, K. B. Kim, R. Sinclair, “Phase equilibria in metal-gallium-arsenic systems: Thermodynamic considerations for metallization materials,” J. Appl. Phys., 61, p.2195-2202, 1987.

37. V. S. C. Len, R. E. Hurley, N. McCusker, D. W. McNeill, B. M.

Armstrong, H. S. Gamble, “An investigation into the performance of diffusion barrier materials against copper diffusion using metal-oxide-semiconductor (MOS) capacitor structures,” Solid -State Electronics, 43, p.1045-1049, 1999.

38. 李世鴻, 半導體工程原理, 全威圖書, p.401-404, 1998.

39. D. L. Smith, “Thin-Film Deposition Principles and Practice,” The

McGraw-Hill Companies Inc., p.483-499, 1999.

40. M. Ohring “The Materials Science of Thin Film,” Academic Press, p.121-123, 1992.

41. 黃振昌, “表面分析儀器-X光光電子能譜儀,” 精密儀器發展中心, p.5-6, 1998.

42. 許樹恩, 吳泰伯, 材料科學叢書1-X光繞射原理與材料結構分析, Chap. 20, p.532-533, 1996.

43. C. D. Wagner, W. M. Riggs, L. E. Davis, J. F. Moulder, G. E.

muilenberg, “Handbook of X-ray Photoelectron Spectroscopy,”

Perkin-elmer Corp., 1984.

44. A. O. Ibidumni, R. L. MaSaitis, R. L. Opila, A. J. Davenport, H. S.

Isaacs, J. A. Taylor, “Characterization of the oxidation of tantalum nitride,” Surface and Interface analysis, Vol. 20, p.559-564, 1993.

圖 2-1 f.c.c 晶體結構

圖 2-2 砷化鎵晶體結構(閃鋅礦結構,zincblende)

圖 2-3 砷化鎵之電子漂移速度圖

圖 2-4 砷化鎵之能隙圖

圖 3-1 濺鍍實驗系統示意圖 substrat

heat cold water ion

shutte

power targe

N2

Ar

mechanica l turbo

pum valv

MFC

圖 3-2 實驗流程架構示意圖 TaNX 膜濺鍍

真空環境封管 鎵氣氛環境封管 砷氣氛環境封管

不同溫度退火

XRD 分析 SEM 分析

XPS 分析 XRD 分析

Cu 膜濺鍍

圖 3-3 真空封管系統架構圖

圖 3-4 真空封管過程示意圖

圖 3-5 置放雜質源的封管示意圖

圖 3-6 出爐時冷卻方法

圖 4-1 鉭基氮化物外層電子 4f7/2和 4f5/2軌域的束縛能(a)Ta(b)

Ta2N(c)TaN

圖 4-2 鉭基氮化物外層電子 4f7/2和 4f5/2軌域的束縛能(a)150W Si

(b)150W Glass(c)200W Si(d)200W Glass

圖 4-3 表 4-2 中 M、N、O、P 組的 X 光繞射圖譜(a) M (200W, 9.5/0.5) (b) N (150W, 9.5/0.5) (c) O (150W, 13/0.5) (d) P (150W, 18/0.5)

圖 4-4 表 4-2 中Ⅰ、Ⅱ、Ⅲ、Ⅳ組的 X 光繞射圖譜(a)Ⅰ(50W, 5/0) (b)

Ⅱ(50W, 5/0.5) (c) Ⅲ(100W, 7.5/0) (d) Ⅳ(100W, 7.5/1)

圖 4-5 表 4-2 中Ⅴ、Ⅵ、Ⅶ、Ⅷ組的 X 光繞射圖譜(a)Ⅴ(150W, 7.5/1) (b)Ⅵ(175W, 6.5/1) (c)Ⅶ(175W, 8.5/1) (d)Ⅷ(200W, 9.5/0.5)

圖 4-6 真空氣氛、不退火情況下的 X 光繞射圖譜(a)無鉭基氮化物 阻礙層(Cu/GaAs)(b)有鉭基氮化物阻礙層(Cu/TaNx/GaAs)

圖 4-7 真空氣氛、不同熱處理一小時下,鉭基氮化物在砷化鎵基板 和銅膜間〔Cu(324nm) / TaNx (141nm) / GaAs〕的 X 光繞射 圖譜(a)未退火(b)500℃(c)600℃

圖 4-8 鉭 基 氮 化 物 在 砷 化 鎵 基 板 和 銅 膜 間 〔 Cu(284nm)/TaNx (212nm)/GaAs〕退火一小時後的 X 光繞射圖譜(a)575℃ (b)

625℃

圖 4-9 鉭基氮化物在玻璃基板上退火一小時後的 X 光繞射圖譜(a)

未退火(b)400℃(c)500℃(d)600℃

圖 4-10 鎵氣氛環境、不同基板〔Cu (284nm)/ TaNx (212nm)/ Sub.〕、

不同溫度下退火一小時後的 X 光繞射圖譜(a)600℃玻璃基 板(b)600℃砷化鎵基板(c)650℃砷化鎵基板

圖 4-11 砷氣氛環境、不同基板〔Cu (284nm)/ TaNx (212nm)/ Sub.〕、

不同溫度下退火一小時後的 X 光繞射圖譜(a)575℃砷化鎵 基板(a1)575℃玻璃基板(b)600℃砷化鎵基板(b1)600

℃玻璃基板(c)650℃砷化鎵基板

(a)

(b)

圖 4-12 真空氣氛下(a)不退火(b)575℃退火一小時後,鉭基氮化 物在矽基板上(TaNx/Si)經酸蝕刻後表面之 SEM 圖

(c)

(d)

圖 4-12(續上)真空氣氛下(c)650℃(d)700℃退火一小時後,鉭 基氮化物在矽基板上(TaNx/Si)經酸蝕刻後表面之 SEM 圖

(a)

(b)

圖 4-13 真空氣氛下(a)575℃(b)700℃退火一小時後,銅膜在鉭基氮化物上

(Cu/TaNx/Si)經酸蝕刻後表面之 SEM 圖

晶格常數( Lattice constant ) 5.65 Å

密度( Density ) 5.317 g/cm3

原子密度( Atomic density ) 4.4279×1022 atoms/cm3

原子量( Molecular weight ) 144.642

線性膨脹係數( Linear expansion coefficient ) 5.73×10-6 K-1

比熱( Specific heat ) 0.327 J/g-K

晶格熱導率( Lattice thermal conductivity) 0.55 W/cm-K 相對介電常數( Relative dielectric constant ) 12.85

能隙( Bandgap ) 1.423 eV

臨限電場( Threshold field ) 3.3 KV/cm

最大漂移速度( Peak drift velocity ) 2.1×107 cm/s 電子遷移率( Electron mobility ) 8500 cm2/V-s 電洞遷移率( Hole mobility ) 400 cm2/V-s

熔點( Melting point ) 1238℃

表 2-1 砷化鎵在室溫時(300 K)之特性

鉭金屬和鉭基氮化物

的種類 結 構 晶格常數

(Lattice parameter)

電阻率

Body-centered

cubic system a = 3.370 Å 80

Ta2N ( ã-phase )

Hexagonal close-packed system

as = 5.283 Å

金屬/砷化鎵 穩定溫度 不穩定

發生溫度 不穩定時產生現象

Au/GaAs - 250℃ Au causes dissociation of GaAs Ga migrates into Au

Pt/n-GaAs - 350℃ PtAs2、PtGa

Ti/GaAs 300℃ 400-500℃

產生 Ti/TixGa1-x/TiAs/GaAs 的結構 低溫退火產生 Ti2Ga3、TiAs

高溫退火產生 Ti5Ga4、Ti5As3

W/GaAs 500-550℃ 600℃

介面附著力變差且存在高應力,使得鎢膜剝 落 (The W film peels off due to poor adhesion and high stress in the interface) Au/TiW/GaAs 600℃-15hr -

WSi0.64/GaAs 850℃ -

MoSi2/GaAs 800℃ -

Si/Ta/Si/GaAs 800℃ 920℃-20min TaSi2

Cu/Ti/GaAs - 350-450℃ CuTi、Cu3Ti

Cu Cubic

CuGa2 Tetragonal

d (A) Intensity(I/I0) (h k l)

1.973 20 212 46.0

Cu5As2 Orthorhombic

d (A) Intensity(I/I0) (h k l)

1.374 50 004 68.3

1.365 10 181 68.8

1.345 40 361 69.9

1.327 60 440/352 71.0

1.316 40 323/402 71.7

CuAs2 Monoclinic

d (A) Intensity(I/I0) (h k l)

Ta Cubic

TaN Hexagonal

d (A) Intensity(I/I0) (h k l)

TaAs Tetragonal

1.330 3 500 70.8

1.320 7 004 71.5

1.298 2 223 72.9

1.272 1 412 74.6

1.257 4 420 75.7

1.248 1 114 76.3

1.244 7 331 76.6

1.227 1 204 77.9

1.195 1 510 80.4

1.188 12 502 80.9

1.169 6 214 82.5

1.152 7 332 84.0

1.134 5 304 85.6

組別 試片 r.f. power

(W) Ar/N2 (sccm) 4f7/2 B.E. (eV)

4f5/2

B.E. (eV) N / Ta (at.)

A TaNx / Si 100 6 / 2 24 25.4 9.99

B TaNx / Glass 100 6 / 2 24.4 26.2 6.63

C TaNx / Si 100 7 / 3.5 24.4 26.2 8.62

D TaNx /Si 100 7 / 3.5 24.2 26.2 8.80

E TaNx /Si 100 8 / 2 24.4 25.8 5.76

F TaNx /Si 100 8 / 2 24.2 25.4 7.00

G TaNx /Si 100 7 / 7 24.6 26.2 11.66

H TaNx / Glass 100 7 / 7 25 27.2 8.35

I TaNx /Si 150 9.5 / 0.5 20.8 22.6 4.04

J TaNx / Glass 150 9.5 / 0.5 22 23.6 4.75

K TaNx /Si 200 9.5 / 0.5 21.2 23 8.56

L TaNx / Glass 200 9.5 / 0.5 21.8 23.4 3.17 表 4-1 XPS 數據整理表格(以上成長壓力均為 2 m torr)

組別 靶材 試片 r.f. power

組別 試片 靶材

表 4-4 EPMA(以上各組成長壓力均為 2m torr)

P 組 Ta N Ta/N

No.1 85.828 14.172 6.056 No.2 88.587 11.413 7.762 No.3 87.452 12.548 6.969 Average 87.289 12.711 6.867 成長條件:150W Ar/N2= 18/0.5 Ta : N = 6.87:1

M 組 Ta N Ta/N

No.1 82.622 17.378 4.754 No.2 83.716 16.285 5.141 No.3 83.311 16.689 4.992 Average 83.216 16.784 4.962 成長條件:200W Ar/N2=9.5/0.5 Ta : N = 4.96:1

相關文件