Atomic Layer Deposition of Hafnium Dioxide Films from Hafnium Hydroxylamide and Water

Kukli, Kaupo; Ritala, Mikko; Leskelä, Markku; Sajavaara, Timo; Keinonen, J.; Jones, Anthony; Tobin, Neil L.

doi:10.1002/cvde.200306281

Cited by 29 publications

(19 citation statements)

References 39 publications

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“…Comparison with reference XRD data [26] shows that the films exist predominantly in the monoclinic phase, unsurprising as the monoclinic phase of HfO 2 is the thermodynamically stable phase under atmospheric pressure, up to temperatures of 1500±1900 C, when it transforms into the tetragonal or orthorhombic form. [27] The deposition of monoclinic HfO 2 observed herein is fully consistent with other MOCVD [6,10] or ALD [28,29] studies using a variety of hafnium oxide precursors, in which monoclinic HfO 2 has been found to be the predominant phase. The microstructure of the HfO 2 films was analyzed using SEM.…”

Section: Introductionsupporting

confidence: 90%

Growth of Hafnium Dioxide Thin Films by Liquid‐Injection MOCVD Using Alkylamide and Hydroxylamide Precursors

Williams¹,

Jones²,

Tobin

et al. 2003

Chemical Vapor Deposition

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4 ]. Varying levels of residual carbon and nitrogen were detected in the films grown from each precursor. Analysis by X-ray diffraction (XRD) indicates that films grown from both precursors exist predominantly in the thermodynamically stable monoclinic phase. Scanning electron microscopy (SEM) shows that the morphology of the HfO 2 films from each precursor is markedly different, with films deposited from [Hf(NMe 2 ) 4 ] having a well-defined columnar crystalline structure, whereas films grown from [Hf(ONEt 2 ) 4 ] are smoother with little evidence of columnar structure. Full crystal structure data for [Hf(NMe 2 ) 4 ] are given, and the dielectric properties of [Al/HfO 2 /n-Si(100)] MOS capacitors, fabricated using each precursor, are also reported.

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Section: Introductionsupporting

confidence: 90%

Growth of Hafnium Dioxide Thin Films by Liquid‐Injection MOCVD Using Alkylamide and Hydroxylamide Precursors

Williams¹,

Jones²,

Tobin

et al. 2003

Chemical Vapor Deposition

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“…This growth rate is comparable to that ob- tained by using Hf(NMeEt) 4 , [15] and much higher than those obtained by using HfI 4 (0.47-0.62 Å per cycle), [8] Hf(ONEt 2 ) 4 (0.5-0.6 Å per cycle), [18] and other hafnium alkoxides [Hf(mmp) 4 (0.2-0.3 Å per cycle) [11,12] and Hf(O t Bu) 2 (mmp) 2 (0.4-0.6 Å per cycle)]. [11,13] The higher growth rate of Hf(mp) 4 compared to those of other alkoxide precursors may originate from the decrease in steric hindrance due to the small size of the mp ligand compared to the bulkier mmp ligand and the relatively high volatility of Hf(mp) 4 .…”

Section: Deposition Of Hfo 2 Filmssupporting

confidence: 72%

“…[20] Deposition temperatures above 300°C were required to obtain high enough growth rates, while the precursors were thermally decomposed at these temperatures. [14][15][16] hafnium nitrate [Hf(NO 3 ) 4 ], [17] and hafnium hydroxylamide [Hf(ONEt 2 ) 4 ] [18] have been investigated for the ALD of HfO 2 .…”

Section: Introductionmentioning

confidence: 99%

ALD of Hafnium Dioxide Thin Films Using the New Alkoxide Precursor Hafnium 3-Methyl-3-pentoxide, Hf(mp)4

Cho

Chung

et al. 2006

Chem. Vap. Deposition

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A new alkoxide precursor, Hf(mp) 4 [mp = 3-methyl-3-pentoxide, OC(CH 3 )(C 2 H 5 ) 2 ] has been employed in the atomic layer deposition (ALD) of HfO 2 thin films using water (H 2 O) as the oxygen source. The self-limiting ALD process via alternate surface reactions of Hf(mp) 4 and H 2 O is confirmed from thickness measurements of the HfO 2 films grown with varied Hf(mp) 4 supply time and number of Hf(mp) 4 /H 2 O ALD cycles. The ALD temperature window for this precursor is found to be between 250 and 350°C. Under optimal reaction conditions, the growth rate of the HfO 2 films is ∼0.9 Å per cycle. Amorphous films can be obtained across the entire temperature range with atomically flat and uniform surfaces. X-ray photoelectron spectroscopy (XPS) and depth-profiling Auger electron spectroscopy (AES) indicate that the films are stoichiometric with negligible amounts (less than 2 %) of carbon impurities.

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“…4 ], [33] [Hf(NR 2 ) 4 ] (R = Me, Et), [34,35] [Hf(O t Bu) 4 ], [36] [Hf(O t Bu) 2 (mmp) 2 ], [37] [Hf(mmp) 4 ] [38] (mmp = 1-methoxy-2-methyl-2-propanolate, OCMe 2 CH 2 -OMe), and [Hf(ONEt 2 ) 4 ]. [39] In this paper we describe, for the first time, the liquid injection ALD [40] produce only lanthanide silicate films, although LaAlO 3 [41] and PrO x [42] …”

Section: Introductionmentioning

confidence: 99%

Deposition of HfO2, Gd2O3 and PrOx by Liquid Injection ALD Techniques

Potter¹,

Chalker²,

Manning³

et al. 2005

Chem. Vap. Deposition

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Thin films of hafnium oxide (HfO 2 ), gadolinium oxide (Gd 2 O 3 ), and praseodymium oxide (PrO x ) have been deposited by liquid injection atomic layer deposition (ALD) and for comparison, have also been deposited by ªthermalº metal-organic (MO) CVD using the same reactor. The ALD-grown films were deposited on Si(100) over a range of substrate temperatures (150±450 C) using alternate pulses of [Hf(mmp) 4 ], [Gd(mmp) 3 ], or [Pr(mmp) 3 ] (mmp = OCMe 2 CH 2 OMe) and water vapor. X-ray diffraction (XRD) analysis showed that as-grown films of HfO 2 were amorphous, but these crystallized into the monoclinic phase after annealing in air at 800 C. XRD analysis showed that as-grown Gd 2 O 3 and PrO x films had some degree of crystallinity. Residual carbon (0.8±3.3 at.-%) was detected in the HfO 2 and PrO x films by Auger electron spectroscopy (AES), but not in the Gd 2 O 3 films. The self-limiting behavior of the precursors was investigated at 225 C by varying the volume of precursor injected during each ALD cycle and, in each case, oxide growth was not fully self-limiting. We propose a mechanism for this involving b-hydride elimination of the mmp group, and also propose some general mechanistic principles which may influence the growth of oxides by ALD using other precursors.

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Atomic Layer Deposition of Hafnium Dioxide Films from Hafnium Hydroxylamide and Water

Cited by 29 publications

References 39 publications

Growth of Hafnium Dioxide Thin Films by Liquid‐Injection MOCVD Using Alkylamide and Hydroxylamide Precursors

Growth of Hafnium Dioxide Thin Films by Liquid‐Injection MOCVD Using Alkylamide and Hydroxylamide Precursors

ALD of Hafnium Dioxide Thin Films Using the New Alkoxide Precursor Hafnium 3-Methyl-3-pentoxide, Hf(mp)4

Deposition of HfO2, Gd2O3 and PrOx by Liquid Injection ALD Techniques

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