High-speed laser direct writing of tungsten conductors from W(CO)6

Nambu, Yasusada; Morishige, Yukio; Kishida, Shunji

doi:10.1063/1.102848

Cited by 22 publications

(5 citation statements)

References 12 publications

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“…We have recently modified MSIMPC48 to calculate temperature-programmed reaction mass spectra. We have used the code to simulate CO desorption during metal hexacarbonyl decomposition from steps [1][2][3][4][5][6] for comparison to experiments on W(CO)6 on W(110).22 The qualitative agreement is quite good considering the crudeness of our mechanism, the main discrepancy being an underestimation of the molecular CO desorption rate between 200 and 300 K. The consistency of the simulations with both LCVD and temperature-programmed reaction data indicates that (l)-( 6) provide a reasonable description of central elements of the reaction. We are currently working to refine our model to include coverage and bonding state effects.…”

Section: Discussionmentioning

confidence: 99%

Visible laser-induced nucleation and growth of chromium, molybdenum, and tungsten films from the hexacarbonyls: reactivity of carbon monoxide on film surfaces

Houle¹,

Singmaster²

1992

J. Phys. Chem.

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Continuous visible laser irradiation is used to deposit Cr, Mo, and W films from the hexacarbonyls by thermal excitation.Detailed analyses of the films by scanning Auger microscopy show that the Mo and Cr films are spatially inhomogeneous, having clean metal centers surrounded by contaminated metal rings. W films are completely pure. Depth profiles reveal that, prior to formation of clean Mo and Cr, an interfacial layer of contaminated material is deposited which becomes progreesively metal rich as thickness increases. If such a layer is formed for W, it is very thin. The measured composition profiles are compared to calculated surface temperature distributions in order to extract information on the kinetics of CO dissociation and desorption during growth. The temperature and mechanism simulations show that CO desorption dominates above about 450 K, ensuring that pure metal is deposited. Below that temperature contamination occurs. Previous investigations of film growth from metal hexacarbonyls have led to the conclusion that film purity will only be high at temperatures exceeding 800 K, where recombinative desorption of CO is fast. The origins of the large discrepancy in temperatures are discussed.Chemical processes leading to growth of metal oxycarbide material at the fdm edges and film-substrate interface are explored using data from the catalysis literature. The strong parallels found between the laserdeposited material and supported catalysts formed from the hexacarbonyls suggest that the oxycarbide films may have significant Lewis acid-base character, leading to faster CO and metal40 bond dissociation rates. Thus, formation of contaminated material appears to depend on local surface composition as well as temperature. Iatroduction, The identification of useful gas-phase precursors for laser-ind u d chemical vapor deposition (LCVD) of the early transition metals Cr, Mo, and W has been a surprisingly inactive area. Since the process uses a laser beam to heat a localized area of the substrate and c a w pyrolytic decomposition of incident molecules, the few precursor systems which have been studied arc those used previously in conventional chemical vapor deposition (CVD) procarpes. By far, the major effort has bem applied to continuous laser deposition from the hexacarbonyl'" and hexafluoride7 of tungsten, with some limited attention to molybdenum hexacarbonyl>8 chromium he~acarbonyl?.~ and the bis(benzene) complexes of Cr and Mo.l0 Film characterization and processhas been on rapid direct writing of small features. It has been shown that film resistivities of Mo and W approach those of bulk material as laser power, and thus surface temperatures, increase.6 The lowest resistivity reported for W, approximately 1-2 times the bulk value for a-tungsten, is obtained using a 355-nm Ar+ laser beam to deposit lines on glass in a cell heated to 360 K.6Surface temperatures are estimated to be 800-1000 K during growth. Although ultraviolet light is used, the photolysis yield of the hexacarbonyls at that wavelength is so s...

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Section: Discussionmentioning

confidence: 99%

Visible laser-induced nucleation and growth of chromium, molybdenum, and tungsten films from the hexacarbonyls: reactivity of carbon monoxide on film surfaces

Houle¹,

Singmaster²

1992

J. Phys. Chem.

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“…In earlier studies, various types of metal carbonyls such as Ni(CO) 4 , Fe(CO) 5 , Cr(CO) 6 , Mo(CO) 6 or W(CO) 6 have been used for metal deposition in the form of microstructures or extended thin films [11][12][13][17][18][19]. In the present study, tungsten carbonyl, W(CO) 6 , was chosen as the reaction material to deposit micrometer-scale tungsten lines.…”

Section: Methodsmentioning

confidence: 99%

“…[11][12][13][14][15]. For an application to a manufacturing line, however, further study is necessary to meet the specific requirements of the manufacturing process and LCD products.…”

Section: Introductionmentioning

confidence: 99%

Hybrid LCVD of micro-metallic lines for TFT-LCD circuit repair

Park¹,

Kim²,

Shin³

et al. 2006

Applied Surface Science

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“…Gaseous WF 6 [3][4][5][6][7][8] and WCl 6 [9] are traditional precursors to form W coatings at high reduction temperatures of >600°C and >1000°C, both precursors form highly corrosive gases to give damages to the equipments. However, tungsten carbonyl (W(CO) 6 ) with a low decomposition temperature is a labile and non-corrosive precursor to obtain tungsten coating or the composite materials [10][11][12][13], whose decomposition temperature can be as low as about 400°C. In our work, W(CO) 6 was used to prepare tungsten coatings on copper matrix via chemical vapor deposition.…”

Section: Introductionmentioning

confidence: 99%

Proposal and research on using tungsten carbonyl-CVD process for making W-coating PFMs and W-tubes

Ren

Zhou

Chen

et al. 2014

Journal of Nuclear Materials

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High-speed laser direct writing of tungsten conductors from W(CO)6

Abstract: Fine structures in the broadened line of distributed feedback lasers under highspeed direct modulation Appl. Phys. Lett. 45, 820 (1984); 10.1063/1.95430High speed electron optics for direct slice writing

Cited by 22 publications

References 12 publications

Visible laser-induced nucleation and growth of chromium, molybdenum, and tungsten films from the hexacarbonyls: reactivity of carbon monoxide on film surfaces

Visible laser-induced nucleation and growth of chromium, molybdenum, and tungsten films from the hexacarbonyls: reactivity of carbon monoxide on film surfaces

Hybrid LCVD of micro-metallic lines for TFT-LCD circuit repair

Proposal and research on using tungsten carbonyl-CVD process for making W-coating PFMs and W-tubes

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