Low Temperature Deposition of TiN Ceramic Material by Metal Organic and/or Plasma Enhanced CVD

Abstract

A review is presented describing the development of TiN-CVD from the classical, high temperature T i C l m 2 process, towards low temperature MOCVD processes. This development is presented from a chemical point of view. In addition to low pressure (LPCVD) and atmospheric pressure (APCVD) thermal processing, also plasma enhanced (PECVD) techniques are described. In the past few years production facilities for good quality TiN layers for wear resistant applications have come on the market. Production facilities for IC-technology applications of CVD-TiN are on the edge of breaking through. For both applications deposition temperatures have been reduced to 500-600% Research developments, have shown even lower deposition temperatures possible for TiN and Ti(C,N) layers. # Metal organic compounds are defined as chemicals containing metal nitrogen or metal oxygen bonds (e.g. Ti(NMep)4), where organometallic compounds have metal carbon bonds (e.g. CpTiC7H7)

Low-temperature MOCVD of chromium carbonitride coatings from tetrakis(diethylamido)chromium and pyrolysis mechanism of this single-source precursor

“…The incorporation of metalloid elements in the film probably originates from decomposition side-reaction of this intermediate. Recent results using the vanadium analog 43 and literature data 7,9,10,16 suggest that this decomposition mechanism probably occurs with other diethylamido complexes of transition metals when they are used as single-source precursors in MOCVD.…”

“…The same complex has been postulated in several reports on the CVD reactions using Ti(NR 2 ) 4 . 7,9,10,16 In both cases, i.e. in solid-state thermolysis and CVD conditions, partial doublebond character has been reported for the C-N bond and the contribution of a structure like 5, which favors removal of EtN=CHMe, has previously been taken into consideration.…”

“…Furthermore, in agreement with many reports on the CVD chemistry of Ti(NR 2 ) 4 , we assume that the intermediate 4 is largely responsible for the carbon incorporation into the films, possibly by the route (ii). 7,9,10,16 Obviously, other mechanisms are possible to explain the increase in carbon content, such as a g-H activation of Cr(NEt 2 ) 4 followed by an a-H activation and leading to an increase in the Cr-C bond order. However the mechanism proposed in Scheme 2 is supported by the identification of the by-products, specially using the vanadium derivative.…”

“…Similarly, in spite of a MN x cluster core, transition-metal dialkylamido compounds, M(NR 2 ) x , were not successfully used as singlesource precursors for the growth of metal nitride, since large amounts of carbon were incorporated into the films, as reported for titanium 6,7 and vanadium. 8 Therefore, deposition of metal nitrides using these precursors requires addition of a large excess of ammonia, as demonstrated for nitrides of titanium, [9][10][11][12][13][14][15][16][17] 18 This MOCVD reaction with NH 3 has been widely investigated in order to understand the formation of nitride 9,10,13-17 but pyrolysis of M(NR 2 ) x without any additive is still unclear. 6,7,16,17,20,21 In this paper, the tetrakis(diethylamido)chromium(IV) complex, Cr(NEt 2 ) 4 (1), has been employed as single-source precursor to deposit chromium carbonitride thin films by MOCVD.…”

Chemical vapor deposition of titanium nitride thin films: kinetics and experiments

“…Particularly, two major chemical systems for the thermal CVD of TiN coatings, TiCl4-N2-H2 and TiCl4-NH3-H2, are used [17]. The temperature range for the first system is 900-1200 °C due to the low reactivity of nitrogen [18]. The temperature range for the second system can be easily lowered to 550-750 °C [12].…”