Benzotriazole as Corrosion Inhibitor for Copper

Mansfeld, F.; Smith, Tony; Parry, E. P.

doi:10.5006/0010-9312-27.7.289

Cited by 211 publications

(86 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Operation of the spectrometer in the static regime is accomplished by limiting the integrated ion dose delivered to the target to less than 10 13 ions per cm 2 , or about 1/100 of a monolayer of total exposure. In this way the effect of ion-beam induced damage on the mass spectra collected is minimized (20).…”

Section: Methodsmentioning

confidence: 99%

“…Thus, ionic movement through the film seems to be the rate-determining step, as similarly observed in metallic oxides. This indicates that the bulk of the growth is neither by a chemisorption [suggested in (13) and (17)], nor, strictly speaking, by a dissolution-precipitation mechanism [postulated in (6)(7)(8)(9)(10)(11)(12)]. The latter prevails only in very acidic conditions (5).…”

mentioning

confidence: 99%

See 1 more Smart Citation

Copper Corrosion With and Without Inhibitors

Brusić

Frisch

Eldridge

et al. 1991

J. Electrochem. Soc.

305

157

View full text Add to dashboard Cite

The utility of copper interconnects may ultimately depend on the ability to protect copper from corrosion. We have studied the capacity of lH-benzotriazole (1H-BTA) to provide a protective and stable surface film able to withstand harsh chemical and thermal environments. The film was characterized with electrochemical techniques, in situ ellipsometry, ex situ time-of-flight static secondary ion mass spectrometry, high-temperature mass spectrometry, and accelerated temperature and humidity tests. Several important passivating film properties (thickness, degree of polymerization, thermal stability, corrosion resistance) depend critically on the details of the film preparation conditions. The best corrosion protection is offered by the thin film formed on an oxidized Cu surface. This film has also shown the slowest growth kinetics and the highest degree of polymerization in the Cu-BTA structure.With more aggressive performance requirements for multilevel interconnections, higher conductivity metals, such as copper, are finding their way into a number of products. Copper is a relatively noble metal. Nevertheless, it reacts easily in ordinary, oxygen containing, environments (1). In view of the limited passivation offered by Cu-oxides, we have studied the effectiveness of organic azoles, such as lH-benzotriazole (1H-BTA), as a general method of controlling Cu degradation. For over 40 years 1H-BTA has been successfully used in the prevention of atmospheric Cu corrosion (2), in packaging, storage and transport, in the reduction of thermal oxidation and, in particular, in the protection of copper under immersed conditions (Ref. (3) and references within). The relevant literature is abundant but not unified in its teaching about bonding, thickness, composition and structure of the resulting film and the nature of its protection.Recent work from our laboratory, based on a combination of electrochemical, ellipsometric, and XPS data, has shown that the spontaneous reaction of Cu and 1H-BTA under a variety of conditions leads to the formation of Cu-BTA (4, 5), with copper being Cu +1 , as reported elsewhere (6-12). The formation of a Cu-N bond was clearly identified from the Cu LMM Auger lines. The film was formed both on an oxidized and an oxide-free Cu surface, in contrast to reports suggesting that the presence of Cu 2 O is a prerequisite for the buildup of 14). The thickness of the film was determined to be 0.5-4 nm in the pH range from 3 to 12, reaching 25 nm only under harsh conditions, i.e., in pH 2. Several recent studies of ultrahigh vacuum deposited 1H-BTA have indeed detected 1H-BTA adsorption on clean Cu metal (14-16). An electrochemical equivalent of such a film was formed in our laboratory at Cu 0 kept in

show abstract

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Copper Corrosion With and Without Inhibitors

Brusić

Frisch

Eldridge

et al. 1991

J. Electrochem. Soc.

305

157

View full text Add to dashboard Cite

show abstract

“…Several researchers have examined the interaction of BTA with copper substrates, both adsorption [12][13][14] and the formation of polymeric CuBTA films, [15][16][17][18][19] albeit over much longer time scales than those studied here. A 1:1 stoichiometric association of Cu with BTA − in adsorbed layers indicates the formation of a Cu͑I͒ species.…”

Section: Chronoamperometry Experimentsmentioning

confidence: 99%

Copper CMP Modeling: Millisecond Scale Adsorption Kinetics of BTA in Glycine-Containing Solutions at pH 4

Choi¹,

Tripathi²,

Dornfeld³

et al. 2010

J. Electrochem. Soc.

View full text Add to dashboard Cite

Millisecond scale benzotriazole (BTA) adsorption kinetics in acidic aqueous solution containing 0.01M glycine and 0.01M BTA have been investigated. Chronoamperometry was used to measure current densities on the surface of a micro-copper electrode in pH 4 aqueous solutions containing 0.01M glycine with or without 0.01M BTA. In the presence of BTA the current density decreased as the inverse of the square root of time for a few seconds due to adsorption of BTA. At potentials above 0.4V saturated calomel electrode the current leveled off after a second or so due to the formation of a Cu(I)BTA monolayer on the copper surface. Based on these data a governing equation was constructed and solved to determine the initial kinetics of BTA adsorption. Analysis shows that material removal during copper chemical mechanical planarization (CMP) in this slurry chemistry occurs mostly by direct dissolution of copper species into the aqueous solution rather than mechanical removal of oxidized or pure copper species and that each interaction between a pad asperity and a given site on the copper removes only a small fraction of the Cu(I)BTA species present at that site.

show abstract

“…Very dilute additive solutions (around 10 -6 M) affect the oxygen cathodic reduction only, mainly by blocking the surface active centres for the reaction: Cu+O 2sol => Cu.O 2ads [31,32]. At higher concentrations (>10 μmole/L for C6 and C4; >100 μmole/L for C1 and BTA), the anodic inhibitor effect prevails on the cathodic one, as shown by both the positive shift of E CORR and E BR values and the increasing anodic curve slope.…”

Section: Discussionmentioning

confidence: 95%

“…At a higher concentration of 10 -4 M, both compounds reduced the cathodic currents by more than two orders of magnitude (Figure 4). The lower homologues (BTA and C1) simply hindered the formation of the cathodic hump ascribed to the presence of adsorbed intermediates formed during O 2 reduction [31,32] up to 10 -4 M concentration. They attained one order of magnitude reduction in the cathodic currents at the higher concentration of 10 -3 M ( Figure 5).…”

Section: ) Coppermentioning

confidence: 99%

Alkyl-benzotriazole derivatives as inhibitors of iron and copper corrosion

Trabanelli¹,

Frignani

Monticelli³

et al. 2015

Int. J. Corros. Scale Inhib.

View full text Add to dashboard Cite

5-Alkyl derivatives of benzotriazole (1-12 carbon atom long alkyl chain) were tested as inhibitors of pure iron corrosion in sulphuric or hydrochloric acid at 25°C and pure copper corrosion in acidic sulphate and saline solutions at 30°C. This series of compounds was more efficient in contrasting copper than iron corrosion and, generally, the longer the alkyl chain the higher the inhibiting performances and the longer the persistency of the inhibiting action. However, due to a decrease in the solubility, the maximum inhibiting effects were produced by the hexyl derivative. In the case of iron, these compounds were more efficient in the hydrochloric acid solution than in the sulphuric one, while for copper they were more effective in the acidic sulphate solution than in the acidic chloride solution. The higher inhibiting effects for copper can be justified by the mode of BTA adsorption, that consists in chemisorption, instead of physisorption occurring on iron.

show abstract

Benzotriazole as Corrosion Inhibitor for Copper

Cited by 211 publications

References 0 publications

Copper Corrosion With and Without Inhibitors

Copper Corrosion With and Without Inhibitors

Copper CMP Modeling: Millisecond Scale Adsorption Kinetics of BTA in Glycine-Containing Solutions at pH 4

Alkyl-benzotriazole derivatives as inhibitors of iron and copper corrosion

Contact Info

Product

Resources

About