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Oxidation
Professor: Edward Yi Chang
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二氧化矽之製程與應用
SiO2: Fabrications and Applications
Silicon dioxide insulating layers are used for
various applications in silicon integrated
circuits. By the functions, it can be divided into
1. electric isolation, and 2. shielding and surface
protection layer for dopant ion implantation or
thermal diffusion. There are two main methods
for growing oxide layer films: thermal growth
and low-pressure chemical vapor deposition.
The picture on the left shows the formation of a
silicon dioxide insulating layer in the active area
using regional thermal oxidation.
二氧化矽絕緣層在矽積體電路中有多種用途。依功能可區分為電性隔離、離子植入或
熱擴散遮屏及表面保護層。氧化層薄膜成長的方式有熱成長及低壓化學氣相沈積兩種
主要方法。上圖即是利用區域性熱氧化法於活性區域形成二氧化矽絕緣層。
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二氧化矽(SiO2)的製作方法有: 熱
氧化法（Thermal Oxidation） 沈
積法（Deposition） 陽極氧化法（
Fabrication Methods for SiO2 Anodization） 電漿氧化法（
Plasma oxidation） 其中較常用的
熱氧化法又可分為: 乾氧化法（Dry
oxidation） 濕氧化法（Wet
oxidation） 水氣氧化法（Steam
oxidation） 摻氯氧化法（
Oxidation with Cl） 而濕氧化法
又有 : 普通濕氧化法及 氫氧合成
濕氧化法
The reaction mechanism in the wet oxidation process can be shown as follows:
2H2O+Si→ +SiO2+2H2. (The original reaction)
2H2+O2→ 2H2O (H2 reacts with O2 at high temperature in tube)
2H2O+Si→ SiO2+2H2 (Secondary reaction occurs before H2O is purged out)
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熱氧化法 熱氧化處理需
要在高溫爐 管區中進行
，爐內溫度控 制在800 -
1000℃。矽晶 圓在爐內
高溫環境下，晶 圓表面
會與通入爐管內之 氧氣
作用而形成二氧化矽 膜
(SiO2)。
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Gate Oxidation
In metal semi-transistors, the
silicon dioxide film under the gate
must be a high-quality insulating
material.
Its basic function is similar to the
dielectric in a capacitor. A voltage
applied to the gate can induce
carriers of opposite polarity in the
wafer surface area under the silicon
oxide layer to form a conductive
channel.
閘極氧化層在金屬半電晶體中，閘極下方的二 氧化矽薄膜必須是
高品質的絕緣材料，其基本功能類似電容器中的介電質，經由施
加於閘極上的電壓，可以在氧化矽層下的晶圓表面區域 誘發出極
性相反的載子，而形成一 條導電通道。
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LOCal Oxidation of Silicon 區域性矽氧化法
(LOCOS) (LOCOS)
在積體電路中，各元
件活動區（active area）
間要彼此電性隔 離。
這種隔離可以用熱氧
化矽來 製作，例如區
域性氧化法（LOCOS）
就是在MOS元件的局
部區域成長氧化層。
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Gate Oxidation
緩衝介質層 進行離子
佈植時，我們 除了使
用光阻來限定離子植入
的區域外，也可 以使
用二氧化矽膜來作離子
植入的遮蔽層，有 時
亦稱為緩衝介質層。
Range of ion-implanted rare earth elements in
Si and SiO2 - https://doi.org/10.1016/S0921-
5107(00)00742-X
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Gate Oxidation
二氧化矽為雜質擴散遮罩作
用 由於二氧化矽對一些擴
散雜 質源有較強的阻擋特
性，因 此在半導體製程中
常利用此 一特性，在二氧
化矽層上先 刻劃出選擇擴
散區的窗口， 使得雜質只
能由窗口區向矽 基板內擴
散，其它區域被二 氧化矽
所遮蔽。
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Gate Oxidation
氧化製程設備介紹 有許多的
製程都是在高溫爐管區完成的，
例如氧化、低壓化學氣相沉積
(LPCVD)、 退火...等。操作
過程首先要將爐管區的載具拉
出 來，之後我們將晶圓放入
載具，再將載具推入爐管中，
進行氧化製程。
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Gate Oxidation
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Thermal Oxidation
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Thermal Oxidation
NC
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Thermal Oxidation
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Structures
2-D Representation
The basic structural unit
is a silicon atom
6 membered rings are the surrounded by four
dominant structures found in oxygen atoms.
SiO2 . Quartz is one crystalline
version.
Short range 10~100A order may exist in Si02, but the
overall structure is amorphous p=2.2gm/cm3 SiO2,
2.65gm/cm3 quartz.
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Properties of Insulators
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Oxidation Growth Kinetics
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Kinetics
• F1 = hG(CG-CS) = flux from gas to surface (1)
where: hG = mass transfer coeff (cm/sec)
CG = oxidant conc. in gas (1/cm3)
CS = oxidant conc. at surface (1/cm3)
• Henry's Law: Co = HPs (2)
where: H= Henry's constant (1/gmcm)
PS = partial pressure of oxidant in gas at surface (gm/cm3)
(This holds for molecular species.
We are assuming 02 or H20 as the diffusing species)
C* = equil. conc. of oxidant in oxide which would be in
equilibrium with PG
C*= HPG
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Parabolic Rate Constant
B = C1 e-E1/kT
(111) or (100) Silicon
Dry O2
C1 = 7.72 x102 um2/hr
E1 = 1.23eV
Wet 02 (95oC Bubbler)
C1 = 2.14 x102 um2/hr
E1 = 0.71 eV
Steam (pyrogenic)
C1 = 3.86 x102 um2/hr
E1 = 0.78 eV
E1 physically corresponds to
diffusion of O2, H2O through
SlO2.
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Linear Rate Constant
B/A = C2e-E2/kT
(111) Silicon {for (100) divide
C2 by 1.68}
Dry O2
C2 = 6.23x106 um/hr
E2 = 2.0 eV
Wet 02 (95oC Bubbler)
C2 = 8.95x107 um/hr
E2 = 2.0 eV
Steam (Pyogenic)
C2 = 1.63 xlO8 um/hr
E2 = 2.05 eV
E2 physically corresponds to Si
- Si bond breaking.
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Temperature Influence
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High Oxide Growth Rate Compared to Dry O2
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Initial Rapid Oxidation in Dry O2
For all temperatures in dry O2,
initial linear growth
exptrapolates back to Xi =
200Å.
In H2O, linear region
extrapolates to Xi = O.
Space charge region built in E field which
theoretically exists near enchances O2 diffusion.
gas-oxide interface and
extends for a distance
known as the extrinsic
N
Debeye length
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Extraction of Rate Constants
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Oxide Thickness Determination
Interference between the light
reflected at the two surfaces
gives a characteristic color to
an oxide of thickness Xo as
tabulated on the next page.
Two other common techniques
to measure Xo involve either on
Ellipsometer which uses
reflected polarized light to
extract Xo and N, or a
Spectrophotometer which uses
reflectivity vs. wavelength data
(4500A - 7800A) to determine
Xo. NCTU CSD Lab
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Impurity Redistribution and Segregation
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4 Possible Cases
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Masking Properties
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In actual practice, experimentally determined curves like
those shown above are used. The Phos. curves apply
for all sources. The Boron curves apply for B2O3. For
B2H6, the Phos. curves should be used.
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Orientation
1.Since Si02 has no long range
structure caused by crystal
orientation of the substrate, diffusivity
or B should not be affected.
2.Chemical reaction at the interface
Si ->SiO2 should be affected by
crystal orientation, i.e. B/A should be
affected.
Note the data on previous figures. B
is independent of oxidation; B/A
varies over a range of 1.7X with
<111> the fastest and <100> the
slowest.
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HCl Oxidation
1.Lower oxide charge density at Si-Si02
interface.
so widely used in MOS devices
2. Greater oxide stability -Na+
3. Improved dielectric breakdown voltage
4. Cl is a metal getter, cleaner oxide.
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Possible effects on Oxidation
Rate
1. H2O +02
2.Cl near interface may affect
reaction rate and
so B/A
3.Cl in oxide may affect
diffusivity and
so B
4.Si etching by Cl or HCI at
high temp
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Data like that shown above seems to indicate that all the
mechanisms listed on the previous page play some role. No
detailed physical model exists at present.
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High Substrate Doping Levels
N type dopants generally
pile-up at the silicon
surface.
If they affect the oxidation
rate it is likely through ks.
B or the diffusivity should
not be strongly affected.
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Note that:
1. As we predicted for the N
type impurities the interface
reaction rate or B/A is
strongly affected by doping
because these impurities
pile up at the silicon surface.
2. The 02 or H2O diffusivity
or B is essentially
unaffected because very
little of the dopant ends up
in the growing oxide layer.
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Note that oxidation of
compensated wafers
(P+ + N-) shows the
mechanism is
electrical.
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Summary
• Basic linear parabolic model works well under a wide
variety of conditions. It runs into problems when 2-D
structures (shaped surfaces) are oxidized, or under
the conditions listed below.
• Si Orientation
- Affects interface reaction or B/A
- B/A proportional to density of "available" Si bonds
• Multiple Species
– To 1 st order, multiple species such as 02/H20 can be
assumed to act in parallel and independently to get overall
rate.
– In general, measured rates are higher than predicted this
way -> interaction does occur
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• HCI
– produces H20 - 02
– B/A affected by CI near Si-SiO2 interface
– B affected by Cl in oxide
– Si etching by HCI or Cl
• High Doping Levels (>1019)
– B/A affected by those dopants which pile up at Si
surface and segregate into the Si
– B affected by those dopants that segregate into the
growing oxide
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Oxidation through
a window in the
oxide
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Selective SiO2
growth using
local oxidation
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Suggested model for Si-SiO2 transition region,
viewed looking into silicon (100) face.
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Si-O Bonding Details
Linkage of tetrahedral
elements gives a quartz-
crystal form. When they
are linkes in a random
Each bond makes an angle maner, amorphous silica
of 109.5o with others. The
results.
separation of Si and O atom
is 1.62Å. NCTU CSD Lab
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(a)The basic strucure of SiO2.
(b) Three-dimensional representation of two neighboring Si04
cells, bridged by an oxygen atom.
(c) Two-dimensional lattice representing vitreous Si02 .
(d) The structure of thermally grown Si02 showing bridging and
non-bridging oxygen atoms and dopant (i.e. network modifier)
atoms. NCTU CSD Lab
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High temperature resistivity of thermal oxide.
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Strained and broken bonds:
(a1) normal Si - O bonds
(a2) strained bond in vitreous silica
(a3) broken bond represented with a trapped electron
(a4) broken bond represented with a trapped hole
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Possible interface defects.
(b) Si dangling bonds
(c) Si-Si stretched bond (or oxygen vacancy)
(d) Si-O stretched bond
(e) impurity al interface
Possible oxide bulk defects
(f) Si dangling bond
(g) Si-Si stretchd bond (or oxygen vacancy)
(h) impurity in SO2 NCTU CSD Lab
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How hydrogen can passivate the dangling bond
at silicon surface
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Names and location of charges associated
with the thermally oxidized silicon structure
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Reaction Path
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Effect of heat treatment on fixed charge density
for (111) surface
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1.Interface trapped charge: Qit
Traps located at the Si-SiO2 interface with energy states in
the silicon forbidden band gap.
The interface is due to dangling bond in the interface and
Si/SiO2 discontinuity.
2.Fixed oxide charge: Qf
Located within ≅30Å of the interface. Qf is positive, caused by
ionic silicon left near the interface, these ions and
uncompleted silicon bond (Si-Si or Si-O) at the interface,
resulted in positive fixed oxide charge. Of can be regarded
as a charge sheet located at the Si-SiO2 interface.
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3.Mobile ionic charges: Qm
Na, k, Li Alkali ions are mobile in the oxide under
high temperature and high voltage operation; which
can be removed by TDCE(C2H2Cl2)
2 C2H2Cl2+5O2 2H2O + 2Cl2 + 4 CO2
2 H2O + 2Cl2 4HCl + O2
4. Oxide trapped charge: Qot
may be positive or negative due to holes or
electrons trapped in the bulk of the oxide. The
charge is associated with defects in the oxide due
to radiation, high current, avalanche injection and
can be annealed out by low temperature
annealing.
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Thermal SiO2 surface
resistance versus humidity.
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Effect of processing on Q for (100) wafers.
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Effect of Processing
Variables on Densities of
Oxide Fixed Charges (Qf)
and Oxidation Induced
Interface States (Qit).
Direction of Arrow
Indicates Increase (Up) or
Decrease (Down) in the
Magnitude of the Charges.
In the Case of Annealing in
Hydrogen. Decrease in Qf
is for High Temperature.
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Oxide thickness versus crystal orientation for a one hour
dry oxidation at 1000oC.
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Oxide thickness versus Oxidation time for silicon
oxidation in dry oxygen at high pressure.
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Oxide thickness versus time for thermal
oxidation of silicon in pyrogenic steam at high
pressure
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Preoxidation Surface Cleaning Solutions
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Schematic of Thermal Oxidation Furnace
Vapor Pressure of Water NCTU CSD Lab
