Mocvd of Copper from New and Liquid Precursors (hfac)CuL, Where L = 1-Pentene, Atms, and Vtmos

1996 ◽  
Vol 427 ◽  
Author(s):  
H. K. Shin ◽  
H. J. Shin ◽  
S. J. Lim ◽  
D. J. Yoo ◽  
N. Y. Oh ◽  
...  
Keyword(s):  
Deposition Temperature ◽  
Free Ligand ◽  
Copper Deposition ◽  
Cu Films ◽  
Temperature Range ◽  
Liquid Precursors ◽  
Pure Cu

AbstractLiquid and volatile (hfac)CuL compounds where hfac = 1,1,1,5,5,5-hexafluoro- 2,4-pentanedionate and L = 1-pentene (1), acetyltrimethylsilane (2), and vinyltri- methoxysilane (3) were newly developed for reproducible copper deposition. During CVD processes, no premature decomposition of the precursor was observed in the source reservoir that contained the mixture of (hfac)CuL and excess free ligand L. Pure Cu films were deposited in the deposition temperature range 180°C ˜ 220°C

Copper Chemical Vapor Deposition using a Novel Cu(II) Precursor for Contact Via Filling Process

2007 ◽  
Vol 990 ◽  
Author(s):  
Hideaki Zama ◽  
Yuuji Nishimura ◽  
Michiyo Yago ◽  
Mikio Watanabe
Keyword(s):  
Chemical Vapor Deposition ◽  
Vapor Deposition ◽  
Hydrogen Reduction ◽  
Reduction Process ◽  
Chemical Vapor ◽  
Molar Ratio ◽  
Cu Films ◽  
Pure Cu ◽  
Substrate Temperatures ◽  
Advanced Generation

ABSTRACTChemical vapor deposition (CVD) of copper using both a novel Cu(II) β-diketonate source and hydrogen reduction process was studied to fill contact vias with the smallest diameter in the 32nm and more advanced generation chip. Pure Cu films were grown under the condition with the product of hydrogen partial pressure and H2/Cu source molar ratio being over 1,000,000. We succeeded in filling the 40-nm-diameter contact vias by optimizing the growth condition of the Cu-CVD in both substrate temperatures and reaction pressures.

Stress development and relaxation in copper films during thermal cycling

1993 ◽  
Vol 8 (8) ◽  
pp. 1845-1852 ◽  
Author(s):  
M.D. Thouless ◽  
J. Gupta ◽  
J.M.E. Harper
Keyword(s):  
Thermal Cycling ◽  
Integrated Circuit ◽  
Temperature Hysteresis ◽  
Copper Films ◽  
Cu Films ◽  
Dislocation Glide ◽  
Temperature Range ◽  
Cu Film ◽  
Relaxation Of Stresses ◽  
Power Law Creep

The reliability of integrated-circuit wiring depends strongly on the development and relaxation of stresses that promote void and hillock formation. In this paper an analysis based on existing models of creep is presented that predicts the stresses developed in thin blanket films of copper on Si wafers subjected to thermal cycling. The results are portrayed on deformation-mechanism maps that identify the dominant mechanisms expected to operate during thermal cycling. These predictions are compared with temperature-ramped and isothermal stress measurements for a 1 μm-thick sputtered Cu film in the temperature range 25–450 °C. The models successfully predict both the rate of stress relaxation when the film is held at a constant temperature and the stress-temperature hysteresis generated during thermal cycling. For 1 μm-thick Cu films cycled in the temperature range 25–450 °C, the deformation maps indicate that grain-boundary diffusion controls the stress relief at higher temperatures (>300 °C) when only a low stress can be sustained in the films, power-law creep is important at intermediate temperatures and determines the maximum compressive stress, and that if yield by dislocation glide (low-temperature plasticity) occurs, it will do so only at the lowest temperatures (<100 °C). This last mechanism did not appear to be operating in the film studied for this project.

Sputtered Cu Films Containing Various Insoluble Substances for Advanced Barrierless Metallization

2007 ◽  
Vol 539-543 ◽  
pp. 3497-3502 ◽  
Author(s):  
J.P. Chu ◽  
C.H. Lin
Keyword(s):  
Thermal Stability ◽  
Leakage Current ◽  
Focused Ion Beam ◽  
Ion Beam ◽  
The Other ◽  
Oxide Semiconductor ◽  
Good Thermal Stability ◽  
Cu Films ◽  
Pure Cu ◽  
Thermal Stability Of

Sputtered Cu films containing various insoluble substances, such as Cu(W2.3), Cu(Mo2.0), Cu(Nb0.4), Cu(C2.1) and Cu(W0.4C0.7), are examined in this study. These films are prepared by magnetron sputtering, followed by thermal annealing. The crystal structure, microstructure, SIMS depth-profiles, leakage current, and resistivity of the films are investigated. Good thermal stability of these Cu films is confirmed with focused ion beam, X-ray diffractometry, SIMS, and electrical property measurements. After annealing at 400°C, obvious drops in resistivity, to ~3.8 μ-cm, are seen for Cu(W) film, which is lower than the other films. An evaluation of the leakage current characteristic from the SiO2/Si metal-oxide-semiconductor (MOS) structure also demonstrates that Cu with dilute tungsten is more stable than the other films studied. These results further indicate that the Cu(W) film has more thermal stability than the Cu(Mo), Cu(Nb), Cu(C), Cu(WC) and pure Cu films. Therefore, the film is suitable for the future barrierless metallization.

The Effects of Processing on the Microstructure of Copper Thin Films on Tantalum Barrier Layers

1995 ◽  
Vol 391 ◽  
Author(s):  
E.M. Zielinski ◽  
R.P. Vinci ◽  
J.C. Bravman
Keyword(s):  
Thin Films ◽  
Grain Size ◽  
Barrier Layer ◽  
Crystallographic Orientation ◽  
Deposition Temperature ◽  
Volume Fraction ◽  
Fiber Texture ◽  
Cu Films ◽  
Barrier Layers ◽  
Two Temperatures

abstractPreferred crystallographic orientation and grain size distribution were characterized as a function of processing for sputtered Cu films on Ta underlayers. The Ta barrier layer was deposited at two temperatures, 30 and 100 °C. Cu was deposited at 30, 150 and 250 °C on the 30 °C Ta, and at 100, 150, 200 and 250 °C on the 100 °C Ta. In the first set of samples, with increasing deposition temperature, the Cu (111) fiber texture grew weaker and the volume fraction of randomly oriented grains increased from 0.23 to 0.74. In contrast, for the films deposited on the 100 °C Ta, with increasing deposition temperature, Cu (111) fiber texture strengthened and the fractions of randomly oriented and twinned grains decreased. Grain size was lognormally distributed in all samples and varied approximately parabolically with deposition temperature. At a given deposition temperature, median grain size in the Cu was larger in the films deposited on the 100 °C Ta. These results will be related to the microstructure of the Ta underlayers. Cu microstructure on the 100 °C Ta is shown to be influenced by textural inheritance from the Ta underlayer. Microstructure of the Cu on 30 °C Ta is discussed in terms of trace contaminants.

Thermal stability of sputtered copper films containing dilute insoluble tungsten: Thermal annealing study

2003 ◽  
Vol 18 (6) ◽  
pp. 1429-1434 ◽  
Author(s):  
C. H. Lin ◽  
J. P. Chu ◽  
T. Mahalingam ◽  
T. N. Lin ◽  
S. F. Wang
Keyword(s):  
Thermal Stability ◽  
Thermal Annealing ◽  
Stacking Fault ◽  
Stacking Fault Energy ◽  
Silicide Formation ◽  
Copper Silicide ◽  
Cu Films ◽  
Cu Film ◽  
Pure Cu ◽  
Thermal Stability Of

This paper describes studies on the thermal annealing behavior of Cu films with 2.3 at.% W deposited on Si substrates. The magnetron cosputtered Cu films with insoluble W were vacuum annealed at temperatures ranging from 200 to 800 °C. Twins were observed in focused ion beam and transmission electron microscopy images of as-deposited and 400 °C annealed pure Cu film, and these twins were attributed to the intrinsic low stacking fault energy. Twins in pure Cu film may provide an additional diffusion path during annealing for copper silicide formation. The beneficial effect of W on the thermal stability of Cu film was supported by the following observations: (i) x-ray diffraction studies show that Cu4Si was formed at 530 °C in Cu–W film, whereas pure Cu film exhibited Cu4Si growth at 400 °C; (ii) shallow diffusion profiles for Cu into Si in Cu–W film through secondary ion mass spectroscopy analyses, and the high activation energy needed for the copper silicide formation from the differential scanning calorimetry study; (iii) addition of W in Cu film increases the stacking fault energy and results in a low twin density.

CVD of Thin Films of Copper and Cobalt from Different Precursors: Growth Kinetics and Microstructure

2000 ◽  
Vol 614 ◽  
Author(s):  
Anil Mane ◽  
K. Shalini ◽  
Anjana Devi ◽  
R. Lakshmi ◽  
M.S. Dharmaprakash ◽  
...  
Keyword(s):  
Thin Films ◽  
Deposition Temperature ◽  
Film Growth ◽  
Growth Parameters ◽  
Metal Films ◽  
X Ray ◽  
Cu Films ◽  
Bulk Electrical Conductivity ◽  
Film Microstructure ◽  
Reactor Pressure

ABSTRACTWe have investigated the growth of thin films of Cu and Co by CVD using the β-diketonate complexes of the metals, viz., the respective acetylacetonates, dipivaloylmethanates, and ketocarboxylates. Film growth rate was measured as a function of CVD parameters such as substrate temperature and reactor pressure. Film microstructure was examined by optical microscopy, XRD, SEM, and STM. Electrical resistivity was measured as a function of temperature and film thickness. It was found that film microstructure is a function of the molecular structure of the precursor and of the other growth parameters. For example, Cu films from Cu(II) ethylacetoacetate comprise uniform, fine grains which result in bulk electrical conductivity at a thickness as small as 75nm. Though grown under nearly the same conditions, Cu films from Cu(II) dipivaloylmethanate are porous, with faceted, large crystallites. Cobalt films from Co(II) acetylacetonate are x-ray amorphous even at a deposition temperature of 450°C. It is possible, by choosing CVD parameters, to obtain metal films with microstructures appropriate to devices and to structures of very small dimensions.

Stress Gradients Observed in Cu Thin Films Induced by Capping Layers

2009 ◽  
Vol 1156 ◽  
Author(s):  
Conal E. Murray ◽  
Paul R. Besser ◽  
Christian Witt ◽  
Jean L. Jordan-Sweet
Keyword(s):  
Deposition Temperature ◽  
Morphological Changes ◽  
Film Surface ◽  
Stress Distributions ◽  
X Ray Diffraction ◽  
Cross Sectional ◽  
X Ray ◽  
Cu Films ◽  
Transmission Electron ◽  
Cu Film

AbstractGlancing-incidence X-ray diffraction (GIXRD) has been applied to the investigation of depth-dependent stress distributions within electroplated Cu films due to overlying capping layers. 0.65 μm thick Cu films plated on conventional barrier and seed layers received a CVD SiCxNyHz cap, an electrolessly-deposited CoWP layer, or a CoWP layer followed by a SiCxNyHz cap. GIXRD and conventional X-ray diffraction measurements revealed that strain gradients were created in Cu films possessing a SiCxNyHz cap, where a greater in-plane tensile stress was generated near the film / cap interface. The constraint imposed by the SiCxNyHz layer during cooling from the cap deposition temperature led to an increase in the in-plane stress of approximately 180 MPa from the value measured in the bulk Cu. However, Cu films possessing a CoWP cap without a SiCxNyHz layer did not exhibit depth-dependent stress distributions. Because the CoWP capping deposition temperature was much lower than that employed in SiCxNyHz deposition, the Cu experienced elastic deformation during the capping process. Cross-sectional transmission electron microscopy indicated that the top surface of the Cu films exhibited extrusions near grain boundaries for the samples undergoing the thermal excursion during SiCxNyHz deposition. The conformal nature of these caps confirmed that the morphological changes of the Cu film surface occurred prior to capping and are a consequence of the thermal excursions associated with cap deposition.

The Solubility of Copper and Its Oxides in Supercritical Steam

1963 ◽  
Vol 85 (1) ◽  
pp. 33-44 ◽  
Author(s):  
F. J. Pocock ◽  
J. F. Stewart
Keyword(s):  
High Pressure ◽  
Oxidation State ◽  
Specific Volume ◽  
Copper Deposition ◽  
High Pressure Turbine ◽  
Narrow Temperature Range ◽  
Temperature Range ◽  
Ph Values ◽  
Copper Solubility

This paper contains a study of the solubility of copper and its oxides in supercritical steam which was undertaken because of difficulties experienced with copper deposition in the high-pressure turbine of the Ohio Power Company’s Philo 6 supercritical steam-generating cycle. This study shows that copper has appreciable solubility in superheated supercritical steam. The extent of solubility is apparently a function of the oxidation state of the metal, with the highest state of oxidation (CuO) showing the greatest solubility. A slightly increased solubility was effected by increasing pH values from ∼7.5 to ∼9.5 with ammonia. It is also shown that copper solubility is principally a function of pressure over the narrow temperature range tested (900–1150 F) probably because this parameter has the greatest effect on specific volume.

Mocvd of Copper from the Solution of New and Liquid Precursor (hfac)Cu(1-pentene)

1998 ◽  
Vol 514 ◽  
Author(s):  
H.-K. Shin ◽  
Y.-H. Cho ◽  
D.-J. Yoo ◽  
H.-J. Shin ◽  
E.-S. Lee
Keyword(s):  
Surface Morphology ◽  
Deposition Rate ◽  
Deposition Temperature ◽  
Pure Copper ◽  
Copper Films ◽  
Vapor Pressures ◽  
Dynamic Vacuum ◽  
Liquid Precursor ◽  
Temperature Range

ABSTRACTIn an attempt to increase the deposition rate, new Cu (I) compounds, (hfac)Cu(1-pentene)(1) and (hfac)Cu(VTMOS)(2) have been synthesized. These species are chartreuse liquids and exhibit sufficient vapor pressures to allow high transport rates.In order to avoid the premature decomposition of the copper precursors during CVD processes, the 50% of free 1-pentene, and VTMOS was added to the compounds 1 and 2 respectively. These mixtures 1 and 2 were used in this study. Approximately 2gm of precursor was used for each experiment. No premature decomposition of the precursor in the source reservoir was observed during CVD processes. It is a sufficiently important result to expect the use of these mixtures in copper CVD to achieve the reproducible deposition.The copper films using these mixtures were deposited in a hot-wall pyrex reactor at a pressure of approximately 10–2 torr under dynamic vacuum. The films deposited at 100°C, 150°C and 200°C from the mixture 1. Pure copper films were deposited from these species. The resistivities 1.8 ∼ 2.1 μΩcm were obtained in the deposition temperature range. SEM revealed that the surface morphology of the films grown in these depositon temperature range was composed of dense film and grains were well connected. The deposition rate at 200°C was 3,500 Å/min.

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