1070-4272/01/7410-1636 $25.00 C 2001 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 74, No. 10, 2001, pp. 1636!1640. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 10, 2001,
Original Russian Text Copyright + 2001 by Dyukov, Kuznetsova, Borilo, Kozik.
AND INDUSTRIAL INORGANIC CHEMISTRY
Film-Forming Capacity of Sn(II), Zr(IV), and Hf(IV)
V. V. Dyukov, S. A. Kuznetsova, L. P. Borilo, and V. V. Kozik
Tomsk State University, Tomsk, Russia
Received March 12, 2001
, and SnHacacCl
O were prepared in the solid state and in enthanol
solutions. The film-forming capacity and thermal stability of these compounds were studied. Films of ZrO
, and SnO
were prepared from film-forming solutions of the corresponding acetylacetonates.
At present there is demand for thin film materials
stable in corrosive media and having good optical
properties. The functional and physicochemical prop-
erties of these films are mainly determined by their
preparation conditions and the nature and composi-
tion of the initial film-forming compound (FFC).
The promising FFCs are b-diketonates . Data on
the thermal stability, volatility, behavior in organic
and inorganic solvents, and film-forming capacity of
Group IV metal b-diketonates are scarce and often
In this work, we studied the film-forming capacity
of zirconium hafnium, and tin acetylaetonates. For
this purpose, we prepared these complexes in the solid
phase and in solution, studied their thermal stability
in air, and prepared ZrO
, and SnO
ethanol solutions of these acetylacetonates.
Zirconium and hafnium acetylacetonates Zr(acac)
were prepared from aqueous solutions
of zirconium and hafnium oxychlorides, respectively,
and acetylacetone (molar ratio 1 : 4) at pH 1.933.5.
The resulting mixture was heated on water bath. The
crystalline precipitate was washed with ice-cold water
and dried in air. Tin(II) acetylacetonate was prepared
from ethanol solution (96 wt % C
OH) of tin(II)
chloride hydrate and acetylacetone (molar ratio 1 : 2).
The zirconium and hafnium content was determined
gravimetrically. The actylacetonate (acac
was determined by absorption of the iron(III) acetyl-
acetonate complex at l
= 550 nm .
The qualitative and quantitative composition of
O was determined by means of X-ray
spectral microanalysis (XSMA)  on a Camebax
Microbeam device at accelerating voltage of 20 keV.
Metallic tin and single-crystal sodium chloride were
used as references. The presence of acetylacetone in
the complex was confirmed by qualitative reaction
with iron(III) .
The compositions of the complexes are presented
in Table 1. Acetylacetone in Zr(acac)
complexes is in the deprotonated enol form. The tin
complex is coordination-unsaturated and contains hy-
dration water and Hacac in the undissociated enol and
keto forms, which were previously detected in an eth-
anol solution acidified with HCl .
The solubility of zirconium, hafnium, and tin ace-
tylacetonates in organic and inorganic solvents was
studied at room temperature. The solubility of anhy-
drous zirconium acetylacetonate in chloroform, aceto-
Table 1. Composition of zirconium and hafnium acetyl-
acetonates and dichloro(acetylacetone)tin(II) dihydrate
Composition, wt % ³ M ³ acac
: ³³ ³
found ³ 18.66 ³ 80.70 ³ 3
calculated ³ 18.72 ³ 81.28 ³
: ³³ ³
found ³ 31.12 ³ 66.74 ³ 3
calculated ³ 31.07 ³ 68.93 ³
O ³³ ³
found ³ 35.97 ³ 3 ³ 26.14
calculated ³ 36.43 ³ 3 ³ 27.79