Tantalum Nitride Atomic Layer Deposition Using (tert-Butylimido)tris(diethylamido)tantalum and Hydrazine

Burton, B. B.; Lavoie, Adrien R.; George, Steven M.

doi:10.1149/1.2908741

Cited by 74 publications

(55 citation statements)

References 63 publications

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“…Hydrogen in the form of ÀCH x is expected to be unreactive towards the precursor. Whether the ligands are removed directly during adsorption or by hydride elimination reactions after adsorption, 30 cannot be concluded from the present data.…”

Section: Discussion On the Reaction Mechanismsmentioning

confidence: 60%

“…They also suggested creation of additional surface groups for precursor adsorption during the reactant step. 30 …”

Section: Discussion On the Reaction Mechanismsmentioning

confidence: 99%

“…For ALD with Ta(N t Bu)(NEt 2 ) 3 and N 2 H 4 it was reported that three out of four ligands were removed during precursor adsorption. 30 However, no quantitative conclusions on the number of ligands released can be drawn from the intensity difference. For example, the higher measured intensity level in this m/z range could be simply due to a relatively higher signal per measured HNMe 2 molecule than the signal per measured Ta(NMe 2 ) 5 molecule.…”

Section: Reaction Products: Precursor Stepmentioning

confidence: 99%

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Reaction mechanisms of atomic layer deposition of TaNx from Ta(NMe2)5 precursor and H2-based plasmas

Knoops

Langereis

Sanden

et al. 2011

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers)Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. The reaction mechanisms of plasma-assisted atomic layer deposition (ALD) of TaN x using Ta(NMe 2 ) 5 were studied using quadrupole mass spectrometry (QMS). The fact that molecule dissociation and formation in the plasma have to be considered for such ALD processes was illustrated by the observation of 4% NH 3 in a H 2 -N 2 (1:1) plasma. Using QMS measurements the reaction products during growth of conductive TaN x using a H 2 plasma were determined. During the Ta(NMe 2 ) 5 exposure the reaction product HNMe 2 was detected. The amount of adsorbed Ta(NMe 2 ) 5 and the amount of HNMe 2 released were found to depend on the number of surface groups generated during the plasma step. At the beginning of the plasma exposure step the molecules HNMe 2 , CH 4 , HCN, and C 2 H 2 were measured. After an extended period of plasma exposure, the reaction products CH 4 and C 2 H 2 were still present in the plasma. This change in the composition of the reaction products can be explained by an interplay of aspects including the plasma-surface interaction, the ALD surface reactions, and the reactions of products within the plasma. The species formed in the plasma (e.g., CH x radicals) can re-deposit on the surface and influence to a large extent the TaN x material composition and properties.

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Section: Discussion On the Reaction Mechanismsmentioning

confidence: 60%

“…They also suggested creation of additional surface groups for precursor adsorption during the reactant step. 30 …”

Section: Discussion On the Reaction Mechanismsmentioning

confidence: 99%

Section: Reaction Products: Precursor Stepmentioning

confidence: 99%

See 1 more Smart Citation

Reaction mechanisms of atomic layer deposition of TaNx from Ta(NMe2)5 precursor and H2-based plasmas

Knoops

Langereis

Sanden

et al. 2011

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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“…Thermal ALD processes using either metal halide or metal-organic precursors in combination with NH 3 always yield the highly resistive Ta 3 N 5 phase because the reducing power of NH 3 is insufficient to reduce the Ta oxidation state from þ 5 to þ 3. 329 Cubic TaN, can be deposited by thermal ALD when N 2 H 4 is used as the reactant 330 or with the help of additional reducing agents such as AlMe 3 or elemental Zn. 329,331 However, these processes employ relatively uncommon reactant gases or additional reducing agent dosing steps, which add significantly more complexity to the deposition process.…”

Section: F More Processing Versatility In Generalmentioning

confidence: 99%

Plasma-Assisted Atomic Layer Deposition: Basics, Opportunities, and Challenges

Profijt

Potts

Sanden

et al. 2011

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

741

537

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Plasma-assisted atomic layer deposition (ALD) is an energy-enhanced method for the synthesis of ultra-thin films with Å-level resolution in which a plasma is employed during one step of the cyclic deposition process. The use of plasma species as reactants allows for more freedom in processing conditions and for a wider range of material properties compared with the conventional thermally-driven ALD method. Due to the continuous miniaturization in the microelectronics industry and the increasing relevance of ultra-thin films in many other applications, the deposition method has rapidly gained popularity in recent years, as is apparent from the increased number of articles published on the topic and plasma-assisted ALD reactors installed. To address the main differences between plasma-assisted ALD and thermal ALD, some basic aspects related to processing plasmas are presented in this review article. The plasma species and their role in the surface chemistry are addressed and different equipment configurations, including radical-enhanced ALD, direct plasma ALD, and remote plasma ALD, are described. The benefits and challenges provided by the use of a plasma step are presented and it is shown that the use of a plasma leads to a wider choice in material properties, substrate temperature, choice of precursors, and processing conditions, but that the processing can also be compromised by reduced film conformality and plasma damage. Finally, several reported emerging applications of plasma-assisted ALD are reviewed. It is expected that the merits offered by plasma-assisted ALD will further increase the interest of equipment manufacturers for developing industrial-scale deposition configurations such that the method will find its use in several manufacturing applications.

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“…Thus very long exposures may be needed to saturate ALD reaction with nitrogen plasma inside holes with high aspect ratios. Hydrazine, N 2 H 4 , is more reactive than NH 3 [62], but is highly toxic and explosive at high concentrations.…”

Section: Types Of Ald Precursors For Non-metalsmentioning

confidence: 99%

ALD Precursors and Reaction Mechanisms

Gordon

2013

Atomic Layer Deposition for Semiconductors

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ALD has become accepted as a reliable tool for production of thin films in the microelectronics industry. Dielectrics and metal electrodes for DRAM capacitors are now routinely produced by ALD, which is the only technique capable of uniformly coating inside the narrow structures required by current technology. Transistors will soon be produced as 3D structures, with requirements for conformal coatings over their increasingly complex surfaces. Metal circuits between transistors are also pushing toward narrower and deeper structures, such as through-silicon vias. In order to extend the use of ALD into these new areas, a greater variety of materials will need to be deposited.Successful use of ALD requires suitable chemical precursors used under reaction conditions that are appropriate for them. There are many requirements for ALD precursors: sufficient volatility, thermal stability, and self-limited reactivity with substrates and with the films being deposited. The precursor vapor should not etch or corrode the substrate or deposited film. In addition, it is easier to produce the required vapors if the precursor is liquid at room temperature, or if it is a solid with a melting point below its vaporization temperature, or if it is soluble in an inert solvent with vapor pressure similar to that of the precursor. Ideally, the precursors should be non-flammable, non-corrosive, non-toxic, non-hazardous, and simple and inexpensive to make. In applications of ALD to microelectronics, precursors with high purity may be required.It is not easy to find ideal precursors that satisfy all of these requirements. When the properties of precursors are inadequate, satisfactory ALD results cannot be achieved.

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Tantalum Nitride Atomic Layer Deposition Using (tert-Butylimido)tris(diethylamido)tantalum and Hydrazine

Cited by 74 publications

References 63 publications

Reaction mechanisms of atomic layer deposition of TaNx from Ta(NMe2)5 precursor and H2-based plasmas

Reaction mechanisms of atomic layer deposition of TaNx from Ta(NMe2)5 precursor and H2-based plasmas

Plasma-Assisted Atomic Layer Deposition: Basics, Opportunities, and Challenges

ALD Precursors and Reaction Mechanisms

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