Optical properties of spray-deposited tin oxide films

Hulya Demiryont; K. E. Nietering; R. Surowiec; F. I. Brown; D. R. Platts

doi:10.1364/AO.26.003803

Applied Optics
Vol. 26,
Issue 18,
pp. 3803-3810
(1987)
•https://doi.org/10.1364/AO.26.003803

Optical properties of spray-deposited tin oxide films

Hulya Demiryont, K. E. Nietering, R. Surowiec, F. I. Brown, and D. R. Platts

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Hulya Demiryont, K. E. Nietering, R. Surowiec, F. I. Brown, and D. R. Platts, "Optical properties of spray-deposited tin oxide films," Appl. Opt. 26, 3803-3810 (1987)

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Abstract

Optical properties of spray-deposited tin oxide (TO) films are studied here. Optical grade TO films were deposited using monobutyl tin chloride and dibutyl tin diacetate solutions. The refractive index and extinction coefficient, n(λ) and k(λ), respectively, and film thickness of TO films are evaluated from spectrophotometric transmittance characteristics examined in the visible and UV regions. Since the interference effects are suppressed by the optical absorption in the near-IR region, both reflectance and transmittance spectra are used to evaluate n(λ) and k(λ) values. Spray-deposited TO films are found to be an indirect band gap material exhibiting an absorption minimum at ∼1.0 μm (k ≲ 10⁻³), an energy gap at ∼3.7 eV. A transition from a bounded electron model to a free electron model occurs at λ ≃ 1.4 μm.

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Solution	Substrate T_s < °C)	Rate	Pressure (PSI)		Label	Remarks

			Exhaust	Nozzle

Monobutyl tin trichloride (MBTC) composition 50% trichloride CH₃OH	Initial: 593 Final: 538	Deposition: 630 (Å/Sec.) Cooling: 14 (°C/min.)	Deposition: 4 Cooling: 9.6	20	Type A	Optic grade films, light yellow tinted in thin film form and interference color for thicker films, high optical transparency, clear deposits, good resistance to abrasion and chemical attack. High electrical conductivity.

Dibutyl tin diacetate (DBDA) composition 50% DBDA 50% CH₃OH	Initial: 593 Final: 538	Deposition: 1150 (Å/Sec.) Cooling: 14 (°C/min.)	Deposition: 4 Cooling: 9.6	20	Type B	Optic grade films, light yellow tinted in thin film form and interference color for thicker films, high optical transparency, clear deposits, good resistance to abrasion and chemical attack. High electrical conductivity.

	Tauc Region	Urbach Region	Excess Absorption Region

			Urbach Tail	Free Electron

Dependenc of α on Photon Energy	$α = \frac{C {(E - E_{g})}^{2}}{E}$ C: proportionality constant E_g: energy gap	$α = α_{o} exp . \frac{(E_{l} - E)}{E_{o}}$ α_o E_l: Urbach focus E_o: width of Urbach region	$α_{ex} (E) = α_{mean .} (E) - α_{o} exp . \frac{(E_{l} - E)}{E_{o}}$ α_ex: excess absorption α_meas.: measured absorpiton	$α (E) = \frac{A λ^{2}}{n (B + C λ^{3})}$ A, B, C: are the constants that can be calculated from eqs. 13, 14, and $γ = \frac{em *}{μ}$ n: refractive index

Spectral regions observed on TO films	E >E_g N.B. $\sqrt{α E - vs - E}$ plot provided two linear regions with two slopes. Extrapolating value of these linear regions gave impurity and energy gap E_im and E_g respectively. E_im = 2.45 eV (Type A films) E_im = 2.1 eV (Type B films) E_g = 3.65 eV	E_exp <E <E_l For type A films: E_exp ≃ 1.4 eV E_l ≃ 2.4 eV For type B films: E_exp ≃ 1.2 eV E_l ≃ 2.0 eV	E_p < E < E_exp E_p: free electron absorption edge (plasma region) E_p ≃ 0.3 eV λ_p ≃ 1.4 μ m for all TO films	E < E_p E_p ≃ 0.9 eV

Solution	Substrate T_s < °C)	Rate	Pressure (PSI)		Label	Remarks

			Exhaust	Nozzle

Monobutyl tin trichloride (MBTC) composition 50% trichloride CH₃OH	Initial: 593 Final: 538	Deposition: 630 (Å/Sec.) Cooling: 14 (°C/min.)	Deposition: 4 Cooling: 9.6	20	Type A	Optic grade films, light yellow tinted in thin film form and interference color for thicker films, high optical transparency, clear deposits, good resistance to abrasion and chemical attack. High electrical conductivity.

Dibutyl tin diacetate (DBDA) composition 50% DBDA 50% CH₃OH	Initial: 593 Final: 538	Deposition: 1150 (Å/Sec.) Cooling: 14 (°C/min.)	Deposition: 4 Cooling: 9.6	20	Type B	Optic grade films, light yellow tinted in thin film form and interference color for thicker films, high optical transparency, clear deposits, good resistance to abrasion and chemical attack. High electrical conductivity.

	Tauc Region	Urbach Region	Excess Absorption Region

			Urbach Tail	Free Electron

Dependenc of α on Photon Energy	$α = \frac{C {(E - E_{g})}^{2}}{E}$ C: proportionality constant E_g: energy gap	$α = α_{o} exp . \frac{(E_{l} - E)}{E_{o}}$ α_o E_l: Urbach focus E_o: width of Urbach region	$α_{ex} (E) = α_{mean .} (E) - α_{o} exp . \frac{(E_{l} - E)}{E_{o}}$ α_ex: excess absorption α_meas.: measured absorpiton	$α (E) = \frac{A λ^{2}}{n (B + C λ^{3})}$ A, B, C: are the constants that can be calculated from eqs. 13, 14, and $γ = \frac{em *}{μ}$ n: refractive index

Spectral regions observed on TO films	E >E_g N.B. $\sqrt{α E - vs - E}$ plot provided two linear regions with two slopes. Extrapolating value of these linear regions gave impurity and energy gap E_im and E_g respectively. E_im = 2.45 eV (Type A films) E_im = 2.1 eV (Type B films) E_g = 3.65 eV	E_exp <E <E_l For type A films: E_exp ≃ 1.4 eV E_l ≃ 2.4 eV For type B films: E_exp ≃ 1.2 eV E_l ≃ 2.0 eV	E_p < E < E_exp E_p: free electron absorption edge (plasma region) E_p ≃ 0.3 eV λ_p ≃ 1.4 μ m for all TO films	E < E_p E_p ≃ 0.9 eV

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Applied Optics