Highly Crystallized Microstalline Silicon Films Grown at High Rate with Efficient Gas Utilization

DY Wei, SQ Xiao, SY Huang, HP Zhou, LX Xu, Y Xu and SY XU
Plasma Sources and Applications Centre, NIE, Nanyang Technological University, Singapore 637616

Outline
• • • • Introduction Experimental setup Results and Discussions Summary

Why solar cells?
---Clean Energy Supply Needed For Quality of Life

Advantages
• Independent from fossil and atomic fuel • Transform the energy of the sun direct into electricity • CO2 free electricity generation • Unlimited availability (sunlight) • Local energy supply possible

Electricity Generation Cost

Lowing the cost

Why microcrystalline Si?
• • • • Better long-wavelength optical absorption Improved stability against light exposure Lower electronic defect density Excellent transport property

Challenges
• • Lower efficiency Lower deposition rate ---A representative deposition rate with a standard PECVD technique is as low as 0.3 Å/s

Why ICP-PECVD?
• High densities of the plasma species, rapid growth rate • Wide window for highly crystalline films • Low plasma sheath potentials (several or tens of volts), reduce ion bombardment • Excellent uniformity of the plasma paramters • Low cost (Low-temperature, low-pressure, low-frequency (460 KHz) )

Outline
• • • • Introduction Experimental setup Results and Discussions Summary

Main process
Substrate Choice

Mono-Si

Glass

Cleaning Procedure acetone RCA HF dip

Deposition uc-Si & Diagnosis ICP QMS

Schematic illustration of the ICP deposition system

Quadrupole Mass Spectrometer(QMS) Diagnosis

Outline
• • • • Introduction Experimental setup Results and Discussions Summary

• The formation process of μc-Si:H thin films by plasma mainly includes three elementary reactions: • Primary decomposition of the precursor gases via electron impact reactions • Secondary gas-phase reactions among the radicals and the source gas molecules • Surface reactions on the substrate • The density of atomic hydrogen flux and the energy of ion species impinging on the growing surface are crucial for the deposition process of μc-Si:H thin films

• H is necessary to etch the a-Si network and helpful to gain a dense uc-Si:H.] • SiH3 is the main contributor to the film growth

• SiHx (1≤x≤2) can disturb the formation of an ordered silicon network when diffuse to the growing surface

• During the discharge, we used QMS spectra measurements to qualitatively determine the discharge composition.

From a-Si to uc-Si: phase transition(1)

---effects of RF power density

Deposition Rate vs Power Density

Figure 1. (a) The growth rate as a function of the inductive rf power density at a constant SiH4 concentration of 19.2% for Gourp I films

Raman

The crystalline volume fraction is calculated using the equation:
c  ( I520  I510 ) / ( I520  I510  I 480 )

Raman spectra of the μc-Si:H films deposited at varied inductive rf power density.

where Ii is the area under the Gaussian centered at i.

Raman crystalline fraction and deposition rate as functions of the inductive rf power density.

XRD patterns of Group I Si:H films deposited at different inductive rf power densities: 16.7, 20.8, 25.0, 31.3, and 41.7 mW/cm3.

The surface morphology of the a-Si:H film deposited at a power density of 16.7 mW/cm3.

The corresponding cross-section view of the μcSi:H film deposited at an inductive rf power density of 31.3 mW/cm3.

A typical plain view of the μc-Si:H film deposited at an inductive rf power density of 31.3 mW/cm3.

From a-Si to uc-Si: phase transition(2)

---effects of SiH4 Concentration

Lower concentration, lower transmittance, wider optical bandgap, and stronger absorption

From a-Si to uc-Si: phase transition(3)

---effects of substrate temperature

(a) A sketch of both crystallinity and Eg as functions of the deposition temperauter; (b) SEM cross-section view of one sample deposited at 500 K.

Outline
• • • • Introduction Experimental setup Results and Discussions Summary

Summary
• The plasma density in our ICP system can be high enough to form microcrystalline thin films with a rate higher than 1 nm/s. • QMS is a helpful tool to diagnose the plasma and design experiments for fabricating uc-Si films. • Rf power density is the key to tune the microstructure and the crystalline ratio, and a gradual transition from amorphous to microcrystalline silicon was achieved. • μc-Si:H films which feature a vertically aligned coneshaped structure without amorphous incubation layer. • SiH4 concentration has little effect on the the crystallinities for almost all films , but can tune the bandgap sensitively. • The higher substrate temperature, the higher crystalline ratio, and the lower bandgap.

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