1. Introduction for PECVD Plasma Enhanced Chemical Vapor Deposition

2. Vacuum level：
Under standard atmospheric pressure
Pressure =1 atm =760 mmHg =760 torr = x 105 Pa (?kg/cm2)
=1013 mbar =14.7 psi =7.6 x 105 micron
According to the different behavior of the size of the gas pressure and gas movement, vacuum divided into five levels： Pa
torr
Rough vacuum
Airflow morphology：Viscous flow
1atm~102 Pa
760~1 torr
Medium vacuum
Airflow morphology：Transition flow
102~10-1 Pa
1~10-3torr
High vacuum
Airflow morphology：Molecular flow
10-1~10-5 Pa
10-3~10-7 torr
Ultra-high vacuum
Airflow morphology：Single-molecule movement
10-5~10-8 Pa
10-7~10-10 torr
less 10-8 Pa
less torr

3. Mean free path
Gas molecules in the movement, each molecule before the collision to other molecules, the average walking distance is called the gas mean free path, usually represented by the symbol 「λ」 , unit is cm. at room temperature 20 ° C （The higher the temperature, molecular motion faster）
Pressure
Mean free path
1 x 10-3 torr
5cm
1 x 10-4 torr
50cm
1 x 10-5 torr 5m
1 x 10-6 torr
50m
1 x 10-7 torr
500m
1 x 10-8 torr
5km
1 x 10-9 torr
50km
1 x torr
500km

4. Vacuum pump operating range
Rough vacuum
Medium vacuum
High vacuum
Ultra-high vacuum
Pressure (mbar)

5. Classification of the vacuum gauge
(一) Divided according to the measuring method:：
1. Direct：The size of the direct measurement of the gas molecules acting on the wall or membrane of the sensing element force, reading is usually nothing to do with the gas species, a rough vacuum regardless of the often used this way.
2. Indirect：Characteristics of the measuring gas in a vacuum, such as thermal conductivity, viscosity, etc., to be converted into pressure, high vacuum regardless of this approach is commonly used in reading and gas type.
(二) Divided on the basis of the work principle ：
1. Mechanical：Wall or membrane of the sensing element to the force acting on a size to determine the size of the pressure.
2. Electronic：Number of different vacuum gas molecules caused by the thermal conductivity, viscosity, ionizing the measured strength of electronic signals converted into the size of the pressure.
(三) Divided according to the measurement range：
1. Rough vacuum: 1 atm ~ 102 Pa, Gauge U-tube、Gauges Bourdon 。
2. Medium vacuum: 102~10-1 Pa, Gauge thermocouple、Gauges capacitance manometer
3. High、 Ultra-high vacuum: 10-1~ Pa Gauges cold cathode、Gauge ionization

6. Sputter CVD PVD AC Sputter
Thin Film Deposition
Sputter
Evaporation
CVD
(Chemical Vapor Deposition)
PVD
( Physical Vapor Deposition)
Reactive Sputter
AC Sputter
DC Sputter

7. PVD thin film growth mechanism
First of all, the atoms reach the substrate must have a vertical movement, atoms in order to “adsorption” on a substrate. these atoms in a chemical reaction to form a thin film substrate. thin film composition atoms in the surface of the substrate diffusion movement, this phenomenon is known as the adatom “Surface Migration”. when the atoms collide with each other combination of the trip atoms, Known as “nucleation”.
Atoms must reach a certain size, the continuous stable growth. therefore, the small clusters will be inclined to each other polymerization, formation of a larger atoms, to cut overall energy. Atoms continue to grow will form the “island”. gaps between the nuclear island need to fill in order of atomic island junction and the formation of the entire continuous film. unable to bonding of atoms and the substrate, will be taken from the substrate surface detachment, to formation of free atoms, this step is called the atomic “desorption”.
Substrate
Adsorption
Chemical
reaction
Desorption
Surface
Migration
nucleation

8. Sputter (PVD)

9. PVD-Sputtering

10. PVD-Sputtering
The frequency of using magnets to scan the film thickness can be controlled, scanningmore the number of film thickness and the thicker.
In general, more suitable for thin film deposition conditions: high substrate temperature, low pressure, clean, smooth and non-reaction with the deposited film and the lattice size similar substrate.

11. Vacuum evaporation, sputtering and ion deposition three kinds of PVD method of characteristics.
PVD Evaporation
Vacuum evaporation
Sputtering
Ion deposition
Ions generated
heat
kinetic
Thin film growth rate
Can improve ( < 75 μm/min)
Pure metal other than low (Cu：1μm/min)
Can improve( < 25 μm/min)
Particle
Atoms, ions
Deposition uniformity
if no gas mix in , and it will be worse
good，but the film thickness uneven
Deposition of metal
YES
Evaporation alloy

12. Vacuum evaporation, sputtering and ion deposition three kinds of PVD method of characteristics.
PVD Evaporation
Vacuum evaporation
Sputtering
Ion deposition
Evaporation heat-resistant compounds
YES
Particle energy
0.1~0.5eV
1~100eV
The impact of the inert gas ion
usually not
Yes，or not because of its shape
Mixing between the surface and layer
Heating (external heating)
Yes and No
Deposition rate 10-9 m/sec
1.67~1250
0.17~16.7
0.5~833

13. Vapor deposition, molecular beam epitaxy and  sputtering PVDcharacteristics comparison
Nature of the 
method
Deposition rate
Large-size control
Precise composition control
Can be deposited materials
Manufacturing cost
真空蒸鍍
(Evaporation)
Slow
Poor
Less
分子束磊晶成長
(MBE)
Excellent
濺鍍(Sputter)
Best
many

14. By Energy Resistance Heat Re induction Glow Discharge Photons
Thin Film Deposition
PVD
( Physical Vapor Deposition)
CVD
(Chemical Vapor Deposition)
By Pressure
APCVD
760 torr
LPCVD
10-1 torr
PECVD
500 mtorr
By Reactor Type
Hot/Cool wall
By Energy Resistance Heat Re induction Glow Discharge Photons

15. 化學氣相沉積五個主要機制： CVD 5 mechanisms
(1) Import the main airstream of the reactants (laminar flow (?))
(2) internal diffusion of reactants
(3) Atomic adsorption
(4) Surface chemical reaction
(5) Resultant outer diffusion and remove 基板
At High temperature
( C))
(4)main airstream
(1)Reactant
SiH4, H2
High concent
(2)internal diffusion
Low concent
(3) Adsorption
(5) outer diffusion
Boundary layer
(6)Chemical reaction

16. Atmospheric pressure chemical vapor deposition(APCVD)
The so-called atmospheric pressure chemical vapor deposition method,
 as the name implies, is the pressure to tap into the atmospheric pressure 
CVD reactor of a deposition, the deposition rate of this method is very fast (high deposition rate),approximately   nm / min. Close to atmospheric pressure(1 atm) the APCVD the operating pressure, 
the pressure of molecular collisions between the high frequency of 
homogeneous nucleation "gas phase reactions likely to occur, and easy to produce particles (easily generate particles). APCVD use in industrial applications are concentrated in the larger particle endure the process, 
such as the protection layer (just for to passivation).

17. APCVD Reactor
Shower head

18. Low-pressure chemical vapor deposition (LPCVD)
Low-pressure chemical vapor deposition during thin film deposition, 
the gas pressure inside the reactor lowered to below about 100 torr. A chemical vapor deposition reaction. Reaction at low pressure, the film deposited by LPCVD method has better step coverage, but the lower
 the frequency of collisions between gas molecules makes the LPCVD
 deposition rate is slow compared to APCVD.
The deposition rate is lower.

19. LPCVD System

20. Plasma enhanced chemical vapor deposition (PECVD)
In the CVD reaction, the decomposition of gas molecules need to have sufficient excitation energy .Plasma enhanced chemical vapor deposition 
method, the reaction gas in an electromagnetic field energy, and a variety
  of chemical reactions in the plasma body quickly, resulting in a short 
period of time to complete the chemical vapor deposition.
Belongs to the non-equilibrium plasma in the PECVD .In the body of such a plasma, the free electrons of the absolute temperature is usually higher than the average gas temperature of 1-2 class times, these high-energy
 electron impact gas molecules of the reactants, excitation and ionization,
resulting in very lively chemical properties of free radicals group. Addition ,
the ions hit the substrate surface, resulting in a more lively surface structure,
there by speeding up the chemical reaction. In order to reduce the reaction
temperature required to reach the lowered energy consumption for heating, in
PECVD share of the weight in the CVD process to gradually become a
major thin film deposition tools in Taiwan, especially for IC wafer BEOL
  metal and dielectric deposition of the plasma membrane.

21. Belongs to the non-equilibrium plasma in the PECVD
Belongs to the non-equilibrium plasma in the PECVD. In the body of such a plasma, free electrons of the absolute temperature is usually higher than the average gas temperature 1-2 class times，Free Electrons have high temperature (energy). They will bomb the reactants and gases. The gases will be ionized. The ionics will be active to react with other ionics.
These high-energy electron impact reactant gas molecules, so that excitation and ionization, and chemical properties of very lively radicals. Addition, ion bombardment to the substrate surface, The ionics will also bomb on the substrate surface. Sometime it help deposition, but Sometime it is a damage.
More lively surface structure, thereby speeding up the chemical reaction. In order to reduce the reaction temperature required to reach the lowered energy consumption for heating, in PECVD share of the weight in the CVD process to gradually become a major thin film deposition tools in Taiwan, especially for IC wafer BEOL metal and dielectric deposition of the plasma membrane.

22. Plasma Enhanced CVD System
Shower head
13.56 MHz/ 60MHz W

23. Various comparative advantages and disadvantages of CVD
Process
Advantage
Shortcoming
Application
APCVD
Simple structure of the reactor
Fast deposition rate
Low temperature process
Step coverage of the poor particle pollution
Low temperature oxide
LPCVD
High-purity
Step coverage excellent
Can be deposited on large area chips
High-temperature process
Low deposition rate
High-temperature oxide
Polysilicon
Tungsten, silicide tungsten
PECVD
High deposition rate
Step coverage
Chemical pollution
Particle pollution
Low-temperature insulator
Passivation layer

24. CVD System

25. CVD System

26. Thin Film - PECVD

27. PECVD在Solar Cell 上的應用 a-Si:H
PECVD way to the deposition of thin films, generally have a high hydrogen content in the case of Hydrogen amount is very a high, because the Plasma in the H atoms with unsaturated bonds, not when the deposition statement of Si and N to form the Si-H and NHkey results. Since H is easily affected by temperature has been released (H will be released at a high temperature), resulting in the instability of the TFT device characteristics.
H in plasma will connected with unsaturated Si and N to become Si-H and N-H
PECVD在Solar Cell 上的應用 a-Si:H

28. Hydrogen treat for SiNx layer
After the g-of SiNx do an H2, Plasma, change the surface structure of g-of SiNx, to fill some of the Dangling Bond, in order to avoid the Channel with α-Si Defect trap caused by Cell Mobility lower

29. Preparation and Properties of amorphous silicon
Thin film deposition method
a-Si and its alloys is the plasma CVD, the heat of CVD, reactive sputtering or optical CVD method, vapor-phase synthesis method to prepare thin films.The use of a-Si solar cell, to the plasma of CVD method prepared, it is the first production method described, followed by optical CVD method, Doping.

30. Plasma CVD method
Materials and gases to stimulate dissociation film
As shown the generated SiHx (x ≦ 3) response (neutral and ionic).These reactions are diffusion to reach 100 to 300.C substrate, on which a variety of reactions (adsorption, detachment, pulled out, insert and surface diffusion process), the formation of a-Si film.
Excitation, Decomposition
Transport
Surface
reaction
Film

31. Commercialization of solar cells using the plasma technology applications
Effect
Passivation
Antireflection
Abosrbers
Contacts
Material
SiNx:H
SiO2
SiO2, TiO2, Si3N4
a-Si:H, Cu, In, Ga, Se, S,CdTe
Al, Ag, NiV, Mo, SbTe, ITO, Ti, Pd, ZnO:Al, i-ZnO
Equipment and technology
PECVD
Sputtering
Evaporation

32. Applied by different generations of solar cells, plasma equipment
Solar cell classification
Applications of plasma devices
Plasma coating membranes
2004
2020
The first generation
Silicon type
PECVD、Etcher
Antireflection film batch coated
93%
50%
Second-generation
Film-type(Silicon、II-VI、III-V)
PECVD、PVD
Transparent conductive film, the metal electrode, the silicon thin film 7%
42%
Third-generation
Nano, organic, dye
PVD、PECVD
SiNx/SiOx film、Transparent conductive filmTiO2/Ta2O5、Metal electrodes 0% 8%

33. Thin film growth
Chip film, the initial covered on the wafer surface, many gas molecules or other child, such as atoms and ions. These particles may be because the 
chemical reaction, the solid particles, and then deposited on the wafer surface; or lose part of the kinetic energy through a surface diffusion 
campaign, the wafer surface adsorbed (absorbed) were deposited. According to the order of occurrence can be divided into the following five steps (a) crystal growth (b) the grain growth and (c) grain coalescence 
(d) seam Road to fill the (e) The deposition film growth.

34. thin film deposition steps
(a) crystal growth (b) grain growth and (c) grain coalescence (get together) (d) The seam Road to fill the gap (e) The deposition film growth (1) physical adsorption on the wafer surface adatom (2) adatom back to the gas phase by absorption of the solution

35. Thin film structure island structure：
In the deposition, when the atoms or molecules are mutually binding capacity than the substrate strong island structure, such as metal insulator, graphite and other substrates.
layer structure ：
As the atoms and the substrate bonding is stronger than the others. The first layer of coverage completed with the second layer of bonding will be weak, such as semiconductor thin film of single crystal growth.
Stranski-Krastanov(S.K.) structure ：
Do the aforementioned model of an intermediate process, the current study such behavior is not fully understood, there may be disturbance to the growth of layered structure due to the binding energy.

36. Residual stress
Within the film and the substrate must have the existence of residual stress (thermal expansion coeff.), residual stress according to their form to distinguish can be divided into two, divided into the two kinds of tensile stress and compressive stress.
The film tensile stress of the role, then the film - substrate will show a concaveshape
Film by the compressive stress of the role, then the film - substrate will show aconvex shape
(a) Tensile stress
(b) Compressive stress

37. VHF-CVD reactor electrode structure
Its structure for the strip-type electrodes, However, due to the spacing of theelectrode structure is very narrow, and therefore will produce a standing wave effect, affecting the quality of thin film growth, the left side of the SignalModulator generated waves phase, the elimination of standing wave effect, in order to improve the filmdeposition quality.

38. Applications of PECVD in TFPV
a-Si:H film quality related to the experimental parameters:
(1) Substrate temperature (2)SiH4/H2 ratio (3)Total gas flow rate (4)RF power density (5)Electrode to substrate distance (6) growth pressure, ……
To increase the growth rate of a-Si:H films , some possible problems:
Increase the power density of the plasma power: increase free radical production rate, but will also enhance the pears bombarded by an increase in film stress.
Increase the gas pressure :the homogenous reaction generates more, the powder easily occur, the plasma will easily generate porous film.
Increase viscosity coefficient of free Radicals: cause free radical surface diffusion will decrease to reduce the decline in film quality.

39. Applications of PECVD in TFPV
a-Si：H thin film deposited by PECVD has lower defect density than by sputter due passivation of dangling bonds by H atoms

40. Applications of PECVD in TFPV
Doped a-Si：H thin film
Doped a-Si：H can be fabricated by mixing PH3 and mixing B2H6 or into SiH4/H2 gas in plasma deposition process.
Conductivity of a-Si：H may be varied more than a factor of108
But doping in a-Si：H inevitable leads to creation of dangling bonds, higher defects density and shorter diffusion length of carriers.

41. Microcrystalline Xicheng film agencies
As raw material, SiH4, SiH3 of SiH4 reaction and very stable, is generally considered the main precursor for the SiH4 there is a proportion of about1/1000.
Hydrogen atoms from SiH4 and H2, but with SiH4 to produce the binding reaction.
Of SiH4 + H → H2 + SiH3 extinguished, there is no hydrogen dilution system,the hydrogen atom is almost impossible to reach the substrate surface. To growthe crystal structure must be about 10 times more hydrogen dilution.
Crystalline deposition of microcrystalline silicon thin film changes with thethickness and hydrogen dilution schematic

42. grain boundary

43. Grain size and shape