晶圓製造和磊晶成長

蕭育仁
NDL
 晶體結構

‧非晶態結構
–原子排列完全沒有重複的結構
‧多晶態結構
–原子排列有一些重複的結構
‧單晶態結構
–原子排列全部以相同結構重複

2
 (A)非晶態結構

晶
界
晶
粒

(B)多晶態結構 (C)單晶態結構
3
 Crystalline Structures

4
 Unit Cell Lattice Parameter Refinement

λ2=0.83
=0 83
wRp=0.026
Rp 0.019
Rp=0.019
nsity (a.u.)
Inten

20 40 60 80
2θ(degree)
Na0.63La0.22Nb0.83Cr0.19O3
(Rietveld full pattern refinement method，Abbreviation Rietveld ) Y.J. Hsiao, Ph.D thesis
 為何要用矽?

‧豐度高, 便宜
‧二氧化矽非常穩定,強介電質,容易在熱
氧化過程中成長一層二氧化矽.
氧化過程中成長一層二氧化矽
‧較大的能隙,操作溫度的範圍較大.

6
 Silicon Properties

名稱 矽

Silicon:

Abundant
26% in the earth

SiO2 strong and

stable:
t bl
insulator;
HF selective
etch;
hard mask
dielectric

Bandgap: 1.12eV

7
 (hkl): for a plane
{hkl}: for planes of equivalent symmetry such as {100} for (100),(010),
((001),
), ((-100,(0-10),(00-1)
,( ),( ) in cubic symmetry.
y y
[hkl]: for the direction of a crystal such as [100] for the x-axis.
<hkl>: for a full set of equivalent directions.

8
 Silicon Crystallography

<100>

共價正四面體
diamond

lattice constant

晶胞:
面心立方(fcc)
<111>

9
 晶體結構與缺陷

<100>晶面的晶圓常用於製作金屬氧化物半導體積體電路，
<111>晶面的晶圓通常用於製造雙載子電晶體和積體電路晶
片，因為<111>晶面的原子面密度較高，所以比較適合高功
率元件。
率元件

<100>晶圓上的蝕刻斑 <111>晶圓上的蝕刻斑
10
 矽晶體缺陷的說明

雜質原子在取代位置上 矽原子

雜質原子在間
矽間隙原 隙位置上
子

空位或肖特基缺陷 法蘭克缺陷
11
 差排缺陷

差排是晶格的幾何缺陷 這可能由晶體提拉的製程過程引起
差排是晶格的幾何缺陷，這可能由晶體提拉的製程過程引起。

12
 晶體結構與缺陷

– 晶圓表面上的缺陷和差排密度必須非常低。
晶圓表面上的缺陷和差排密度必須非常低
• 矽表面缺陷

• 矽的懸浮鍵
– 會束縛雜質原子使其無法移動。晶圓背面的缺陷是
刻意製造用於捕獲晶圓內部的污染粒子，以防止這
些會移動的雜質影響微電子元件的正常工作。
些會移動的雜質影響微電子元件的正常工作
 從砂到晶圓

• 石英砂的主要成份是二氧化矽
• 從砂到冶金級矽 (MGS)
• MGS 粉末放進反應爐和氯化氫反應生三氯矽烷
(
(TCS)
)
• 經由汽化和凝結過程純化三氯矽烷
• 三氯矽烷和氫氣反應生成電子級矽材料 (EGS)
• EGS熔化和晶體提拉

14
 從砂到晶圓(續)

‧端末切除,
端末切除 側面拋光,
側面拋光 以及磨出平面或是缺口的
部分
‧從晶棒到晶圓切片
‧邊緣圓滑化,, 研磨,, 濕式蝕刻製程和化學機械研
磨製程(CMP)
雷射畫線(Laser scribe)
‧雷射畫線(Laser
‧磊晶沉積

15
 From sands to silicon

heating
SiO2(石英砂) + 2C(煤) Si (MGS) + 2CO
heating (300℃)
Si + 3HCl SiHCl3(三氯矽烷) + H2 (純度:九個9)

heating (1100℃)
SiHCl 3+ H2 Si (EGS) + HCl

16
 電子級矽材料

資料來源:
http://www fullman com/semiconductors/ polysilicon html
http://www.fullman.com/semiconductors/_polysilicon.html

17
 晶體提拉:查克洛斯基(CZ)法

單晶矽種晶
石英坩堝
單晶矽矽棒

融熔的矽 加熱線圈
1415 °C

石墨坩堝

18
 Crystal
y Growth

• Czochralski (CZ) Process

is a Technique in Making
Single-Crystal
g y Silicon
• A Solid Seed Crystal is 1415oC
Rotated and Slowly
Extracted from a Pool of
Molten Si
• Requires Careful Control
to Give Crystals Desired
Purity and Dimensions
• Large size and low cost

quartz

cf. FZ method

19
 Cylinder of Monocrystalline

• The Silicon Cylinder is Known

as an Ingot (矽錠)
• Typical Ingot is About 1 or 2
Meters in Length
• Can be Sliced into Hundreds
of Smaller Circular Pieces
Called Wafers
• Each Wafer Yields Hundreds
or Thousands of Integrated
Circuits

20
 懸浮帶區法(FZ Method)

多晶矽 融熔矽
棒
加熱線圈移動
加熱線
圈

單晶矽

種晶

21
 兩種方法的比較

• 查克洛斯基法是較常用的方法
– 價格便宜
– 較大的晶圓尺寸 (直徑300 mm )
– 晶體碎片和多晶態矽再利用
• 懸浮帶區法
– 純度較高(不用坩堝)
– 價格較高,
價格較高 晶圓尺寸較小 (150 mm)
– 分離式功率元件

22
 矽晶棒拋光 平邊或 刻痕
矽晶棒拋光,平邊或

平邊, 150 mm和更小尺寸 刻痕, 200 mm和更大尺寸

23
 晶圓切片處理

刻痕方向 冷卻液

晶體晶棒
鋸刀 晶棒移動

鑽石薄層

24
 不同晶圓尺寸的晶圓厚度

晶圓尺寸(mm) 厚度(μm) 面積(cm2) 重量(grams)

50.8(2吋) 279 20.26 1.32
76 2(3吋)
76.2(3吋) 381 45 61
45.61 4 05
4.05
100 525 78.65 9.67
125 625 112.72 17.87
150 675 176.72 27.82
200 725 314.16 52.98
300 775 706.21 127.68

25
 晶圓邊緣圓滑化處理

晶圓移動
晶圓

邊緣圓滑化前的晶圓

邊緣圓滑化後的晶圓

26
 晶圓研磨

‧粗略研磨
‧傳統的研磨劑,泥漿研磨
‧移除表面大部分的損傷
‧產生平坦的表面

27
 濕式蝕刻製程

‧移除晶圓表面的缺陷
‧將硝酸 (水中濃度79% )), 氫氟酸(水中
濃度49% ), 和純醋酸 依照4:1:3 比例
混合.
混合
‧化學反應式:
3Si + 4HNO3 + 6HF → 3H2SiF6 + 4NO +
8H2O

28
 化學機械研磨製程

壓力
研磨液
晶圓夾具
晶圓

研磨墊

29
 200 mm的晶圓厚度和表面平坦度的變化
76 mm
晶圓切片之後
914 mm

76 mm
邊緣圓滑化之後 914 mm
12.5 mm
粗磨之後 814 mm
<2.5 mm
蝕刻之後 750 mm
幾乎是零缺陷的表面
CMP 之後 725 mm
30
 磊晶成長

‧定義
定義
‧目的
‧磊晶硬體設備
‧磊晶製程

31
 磊晶 定義
磊晶：定義

• 源自於希臘的兩個字
• epi: 在某物之上
• taxies: 安排好的，有秩序的

• 磊晶沉積製程是在單晶基片上生長一層薄
的單晶層.

32
 磊晶 目的
磊晶：目的

• 雙載子電晶體的載體層
– 當維持在高集崩潰電壓時，降低集極電阻.
當維持在高集崩潰電壓時 降低集極電阻.
– 僅磊晶層.
• 因為比晶圓晶體有較低的氧碳濃度
因為比晶圓晶體有較低的氧碳濃度，可增 可增
強動態隨機記憶體(DRAM)和互補型金氧半
電晶體積體電路(CMOS IC)的性能

33
 矽磊晶層在雙載子電晶體的應用

射極 基極 集極
Al•Cu•Si
SiO2
n+ p n+
p+ p+
N型磊晶層
電子流
n+ 深埋層
P型晶片

34
 矽磊晶層在CMOS的應用

金屬 1,
1 Al•Cu

W
BPSG

STI n+ n+ USG p+ p+
P型井區 N型井區
P型磊晶矽
P型晶圓

35
 矽源材料氣體

矽烷 SiH4
二氯矽烷 DCS SiH2Cl2
三氯矽烷 TCS SiHCl3
四氯化矽 SiCl4

36
 氣相摻雜物

氫化硼 B2H6
三氫化磷 PH3
砷化氫 AsH3

37
 矽磊晶層的成長與摻雜製程

SiH2Cl2
AsH3

H2
HCl
Si A H3
AsH

As H

38
 磊晶矽薄膜成長速度與溫度關係
溫度 (°C)
1300 1200 1100 1000 900 800 700
1.0

0.5
SiH4
0.2 質量傳輸控制
區
0.1 SiHCl3

0.05
表面反應控制區
0 02
0.02 SiH2Cl2

0.01
0.7 0.8 0.9 1.0 1.1
39
1000/T(K)
 筒狀式反應器

輻射加
熱線圈
晶圓

40
 垂直式反應器

晶圓

反應物
加熱線圈

反應物及副
產品
41
 水平式反應器

加熱線圈

晶圓
反應物
反應物及副
產品

42
 磊晶製程, 批次系統

• 氫氣沖洗, 溫度升高
• 氯化氫清潔反應器
• 磊晶薄膜成長
• 氫氣沖洗, 溫度冷卻
• 氮氣沖洗
• 打開反應室, 晶圓卸載和再裝載

43
 單晶圓反應器

• 密封反應室, 氫氣圍繞
• 一主機可以有多個反應室
• 較大的晶圓尺寸(到 300 mm)
)
• 均勻的控制性較佳

44
 單晶圓磊晶系統
熱輻射 加熱燈管

晶圓

反應物

反應物與副
產品

石英窗
石英舉升 口
支 架
45
 為何用氫沖洗

• 大部分氮氣做為沖洗的氣體
• 氮相當穩定且豐度高
• 超過攝氏1000 °C, 氮可以和矽反應
• 氮化矽在晶圓表面會影響磊晶矽沉積製程
• 因此氫氣被用來吹除淨化磊晶反應室
• 藉由與晶圓表面的污染物形成氣態的氫化
物來清潔晶圓表面

46
 磊晶層可能的缺陷

表面成核造成堆疊 由基片堆疊錯誤造成
錯誤 的堆疊錯誤

差排 雜質微粒
尖凸物
磊晶層

基片

在 S.M. Zse＇s 超大型積體電路技術之後

47
 Defects in epitaxial layers

Point defects (Vacancies, Interstitials, impurities)

Line defects (Dislocations);
Planar defects ((Stackingg faults,, Boundaries))
Volume defects (Precipitates, Hillocks, Voids)

Usually caused by:

Substrate surface quality and cleanness; Purity of gas sources; Growth
48
conditions (growth rate, temp etc.); Film Properties.
 Point defects

(a) Substitutional impurity.

(b) Interstitial impurity
impurity.
(c) Lattice vacancy.
(d) Frenkel-type defect
(成對產生).
(成對產生)

49
 Chemical vapor
p deposition
p (CVD)
( )

Technology of choice for Si epitaxial growth in production environment:

CVD sometimes denoted vapor phase epitaxy(VPE))

Hydrogen (H2) carrier gas

Reactants: SiCl4, SiHCl3, SiH4, + dopant gases (AsH3, B2H6…)
HCl for selective growth and/or chamber cleaning
N2 for purge REACTION
CHAMBER

WAFER (Tg)
GAS GAS
INLET EXHAUST
SUSCEPTOR

Schematic illustration of a typical

yp VPE p
process

A typical
yp CVD consists of : 1. g
gas handling
g system;
y ; 2. reaction chamber;;
3. heating system; 4. exhaust system and safety apparatus

50
Basic Si CVD types (both batch and single
single-wafer
wafer rectors)

APCVD (atmospheric pressure CVD)

Only for HT epitaxy (e.g.
(e g p-epitaxy
p epitaxy on p+ bulk)

Pressure sensor

LPCVD (low
(low-pressure
pressure CVD)
Deposition around 10-100 torr, e.g. for n+ HT
epitaxy,

UHVCVD (ultra-high vacuum CVD)

Deposition
p around 10-3-10-4 torr. For LT SiGe
epitaxy, (NSEG or SEG)

51
 Si CVD sources and basic reactions for HT epitaxy

Silicon tetrachloride: SiCl4 + H2 ֞ Si + 4HCl (1200°C)

) SiHCl3 + H2 ֞ Si + 3HCl ((1150°C))
Trichlorosilane ((TCS):
Dichlorosilane (DCS): SiHCl2 ֞ Si + 2HCl (1100°C)
Silane: SiH4 ֜ Si + 2H2 (1050°C)

HT epitaxy: TCS or DCS

LT epitaxy: DCS or silane

52
 Doping in Si epitaxy

• Dopants can be added to the gas stream to control the electrical

characteristics of the epitaxial layer
• For
F silicon:
ili
– n-type dopants: AsH3, PH3
– p-typeyp dopant:
p B2H6
• Typically introduced in a very dilute form
• n-type doping may significantly lower the epitaxial growth rate
• p-type
p type doping may significantly increase the epitaxial growth rate

• Dopant incorporation dependent upon dopant/Si

ratio
i iin gas phase, T, growth rate, reactor geometry.

53
 Molecular beam epitaxy (MBE)

Basics: The expitaxial layer is formed by the impingement of molecular or atomic beams of constituents
upon
p the substrate surface in a high g vacuum chamber. The atomic/molecular
/ beams from the cells are
usually formed by thermal excitation, i.e. heating the effusion cells.

Schematic of Si MBE growth

system
(Ref: VLSI Technology, S.M. Sze, 1988)

54
 Metal Organic Chemical Vapor Deposition (MOCVD)
Metal-Organic

The expitaxial layer is formed by the reaction between hydride species such as NH3, AsH3,
and metalorganic species such as Tri-methyl Ga (TMG), Tri-methyl Indium (TMI), Tri-methyl
Aluminum (TMA) etc. Note all these are vapor, hence this technique is a subset of the CVD
technique. Mainly for III-V Epitaxy such as GaAs, GaP, GaN

MOCVD equipment Schematic diagram of the MOCVD process

55
 V
Vapor pressure off mostt common MO compounds
d

Compound P at 298 K A B Melt point

(torr) (oC)

(Al(CH3)3)2 TMAl 14.2 2780 10.48 15

Al(C2H5)3 TEAl 0.041 3625 10.78 -52.5
Ga(CH3)3 TMGa 238 1825 8.50 -15.8
Ga(C2H5)3 TEGa 4.79 2530 9.19 -82.5
In(CH3)3 TMIn 1.75 2830 9.74 88
In(C2H5)3 TEIn 0.31 2815 8.94 -32
Zn(C2H5)2 DEZn 8.53 2190 8.28 -28
Mg(C5H5)2 Cp2Mg 0.05 3556 10.56 175

Log[p(torr)]=B-A/T
56
 Metalorganic bubblers

57
 The dangerous sources for III-V
III V MOCVD

(TBA, CH3)3CAsH2 )

LC50: 半致死濃度，指經由呼吸曝露而導致50 %受測動物死亡時的空氣中毒物濃度。

IDLH:立即危害濃度。
TLV: 室內空氣中最高允許濃度。

58
 Thin-Film
Thin Film Analysis Techniques
Film Thickness Measurement
–Transmission Electron Microscopy (TEM)
–Spectroscopic Ellipsometry (SE)
–X-ray Reflectivity (XRR)
–X-ray Diffraction (XRD)
–Secondary Ion Mass Spectrometry (SIMS)
–Auger Electron Spectrometry
–Rutherford Backscattering Spectrometry (RBS)
Surface/Interface Roughness
–X-Ray Reflectivity (XRR)
–Atomic Force Microscopy (AFM)
–Transmission
Transmission Electron Microscopy (TEM)
59
Elemental Composition
–X-ray Fluorescence (XRF)
–X-ray Diffraction (XRD)
–Auger Electron Spectrometry
–Spectroscopic Ellipsometry (SE)
–Secondary Ion Mass Spectrometry (SIMS)
–Rutherford Backscattering Spectrometry (RBS)
–Energy Dispersive Spectroscopy (EDS/TEM)
Defect Density Inspection
–Transmission Electron Microscopy (TEM)
–Infrared Photoluminescence (PL)
–Schimmel
Schimmel Etch (for Etch Pit Density)
 X-ray Diffraction (XRD)

• With XRD, you can determine how much of 
each phase is present
each phase is present.
• The ratio of peak intensities varies linearly as a 
function of weight fractions for any two phases 
i
in a mixture
i t
• This method is fast and gives semi‐quantitative 
results. M(%) ( )= Im (121)+Im (121) ×100%
Im (121)+Im (121)+Io (121)

Y.J. Hsiao et al, J. Lumin. (2007)

 XRD
ZnNb2O6
K ∗λ
D=
β ∗ cos θ B
D = Size of crystallite
K = constant dependent on crystallite shape (0.89)
λ = x-ray wavelength
β = FWHM (full width at half max) or integral breadth
θB = Bragg Angle
When to use Scherrer’s Formula?
• Crystallite size <1000 Å.
• Peak broadening assured due to crystallite size.
• Within 20%‐30% accuracy at best.
FWHM

y (a.u.)
((Crystallite size is different than particle size)
y p )
Intensity
By an Arrhenius equation:
dln K = Q
dT RT 2 46.7
46.8
46.9
47.0
47.1
47.2
47.3
47.4
47.5
47.6
47.7
47.8
47.9
2θ(deg.)
Q : is the activation energy Y.J. Hsiao et al, Mater. Lett. 64 (2010)
 Transmission Electron Microscopy (TEM)

Capabilities
– Multi-layer thickness capability
– Excellent defect detection
– Elemental composition (with EDS)
Advantages
– Provides accurate film thickness
– Excellent contrast between films
– Provides film interface information
– Provides
P id iinformation
f ti on crystallinity
t lli it
– High resolution (higher than SEM)
Disadvantages
– Destructive; samples need thinning
– Specimen preparation is time and labor
intensive
– Image artifacts require expert
interpretation of micrographs
– Samples may be sensitive to electron beam
damage
– Sample may not be representative TEM image of a Ge/SiGe/Si sample

Appl. Phys. Lett., Vol. 72 (1998) 1718

62
TEM pattern

((a)) TEM images

i off as-
synthesized nanorods at 700
°C.
(b) High-resolution TEM
image of the nanorod and
electron diffraction pattern.
p
(c) as-synthesized
hexagonal microdisk at 900
°C
C.
(d) Electron diffraction
pattern of the hexagonal
nanodisc corresponding
along Ba5Nb4O15 [0001]
zone axis.

Y.J. Hsiao et al, J. Am. Ceram. Soc. (2007)

 Secondary Ion Mass Spectrometry (SIMS)

Capabilities
C biliti
– Elemental composition and film
thickness
– Determination of dopant profiles
– Identification of surface and bulk
contaminants, C, O etc.
Advantages
– ppm/ppb detection sensitivity
– All elements detectable (H to U)
– Compositional maps are
attainable
Disadvantages
– Destructive SIMS depth profile of an as
as-grown
grown SiGe:C base for a HBTs
– Quantifiable only with standards
– Isobaric mass interferences
Applied
pp Surface Science 224 ((2004)) 18–23

64
 At i Force
Atomic F Microscopy
Mi (AFM)

Capabilities
C biliti
– Provides high-resolution surface
roughness
and atomic str
structure
ct re measurements
meas rements
Advantages
– No sample preparation required
Disadvantages
– Small sampling area
– No chemical information provided
– Time
Time-intensive
intensive Surface morphology
p gy of a 1.0 μ
μm
Si0.75Ge0.25 layer grown on Si susbstrate
– Resolution affected by tip wear

AFM image of Ge/Si quantum dot array

65
 磊晶的未來趨勢

• 大晶圓尺寸
• 單晶圓磊晶成長
• 降低磊晶成長的溫度
• 超高真空(UHV, 到 10-9 托)
• 選擇性磊晶

66