JP2005171291A - Titanium-containing thin film and method for producing the same - Google Patents
Titanium-containing thin film and method for producing the same Download PDFInfo
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Abstract
【課題】ＭＯＣＶＤ法により均一で安定した気化を行うことができ所望のチタン含有薄膜を得ることができるチタン含有薄膜の製造方法、及びその方法で得られたチタン含有薄膜を提供する。
【解決手段】式（１）
【化１】
（式中、Ｒ１、Ｒ２はメチル基またはエチル基であり、Ｒ３が炭素数１〜４の直鎖又は分岐状アルキル基の場合、ｋは１から５の整数であり、Ｒ３がトリメチルシリル基の場合、ｋは１から３の整数である。ｍは１から２の整数、ｎは１から３の整数でｍ＋ｎが３又は４となる数を示す。）で示されるチタン錯体を原料として有機金属化学蒸着法によりチタン含有薄膜を製造する。
【選択図】 図１
The present invention provides a method for producing a titanium-containing thin film capable of obtaining a desired titanium-containing thin film by performing uniform and stable vaporization by MOCVD, and a titanium-containing thin film obtained by the method.
SOLUTION: Formula (1)
[Chemical 1]
(In the formula, R 1 and R 2 are a methyl group or an ethyl group, and when R 3 is a linear or branched alkyl group having 1 to 4 carbon atoms, k is an integer of 1 to 5, and R 3 is In the case of a trimethylsilyl group, k is an integer from 1 to 3. m is an integer from 1 to 2, n is an integer from 1 to 3, and m + n is a number that is 3 or 4. A titanium-containing thin film is produced by a metal organic chemical vapor deposition method.
[Selection] Figure 1
Description
本発明は、半導体装置の配線に用いられるアルミニウムまたは銅薄膜を形成加工する際の下地バリアとして有用な、チタン含有薄膜及びそれを有機金属化学蒸着（Ｍｅｔａｌ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ、以下、ＭＯＣＶＤという。）法により製造する方法に関するものである。 INDUSTRIAL APPLICABILITY The present invention is a titanium-containing thin film and a metal organic chemical vapor deposition (hereinafter referred to as MOCVD) useful as a base barrier when forming and processing an aluminum or copper thin film used for wiring of a semiconductor device. The present invention relates to a method of manufacturing by a method.
アルミニウム（以下、Ａｌという。）、アルミニウム系合金、銅（以下、Ｃｕという。）、又は銅系合金は、高い導電性などからＬＳＩの配線材料として応用されている。Ａｌの場合、直接シリコン酸化基板上に接触させると合金化やシリサイド化が起こり、シリコン酸化基板に導電性物質が侵入しリーク電流が著しく増加するという問題があった。Ｃｕの場合も、直接シリコン酸化基板上に接触させるとＣｕ自身が基板内に容易に拡散しリーク電流が著しく増加するという問題があった。 Aluminum (hereinafter referred to as Al), aluminum-based alloy, copper (hereinafter referred to as Cu), or copper-based alloy is applied as an LSI wiring material because of its high conductivity. In the case of Al, when it is brought into direct contact with a silicon oxide substrate, alloying or silicidation occurs, and there is a problem that a conductive material penetrates into the silicon oxide substrate and a leakage current increases remarkably. In the case of Cu as well, when it is brought into direct contact with the silicon oxide substrate, there is a problem that Cu itself is easily diffused into the substrate and the leakage current is remarkably increased.
そこで、Ａｌ，Ｃｕにより配線を形成する際には、ＡｌやＣｕの薄膜とシリコン酸化基板の間に下地バリア薄膜を形成することにより、Ａｌ化合物，Ｃｕの拡散を防止している。この下地バリアメタル薄膜として高融点の金属窒化物である窒化チタン（以下、ＴｉＮという。）膜が知られている。現在までのＭＯＣＶＤ法によるＴｉＮ膜の作製例は、テトラキスジメチルアミノチタン（以下、ＴＤＭＡＴという。）錯体、テトラキスジエチルアミノチタン（以下、ＴＤＥＡＴという。）を原料に用いて行われた例がほとんどである（例えば特許文献１，２参照）。 Therefore, when the wiring is formed from Al or Cu, the base barrier thin film is formed between the Al or Cu thin film and the silicon oxide substrate to prevent the Al compound and Cu from diffusing. As this underlying barrier metal thin film, a titanium nitride (hereinafter referred to as TiN) film which is a high melting point metal nitride is known. To date, most of the examples of the production of TiN films by MOCVD are performed using tetrakisdimethylaminotitanium (hereinafter referred to as TDMAT) complex and tetrakisdiethylaminotitanium (hereinafter referred to as TDEAT) as raw materials ( For example, see Patent Documents 1 and 2).
しかし、上記原料でＴｉＮ膜をＭＯＣＶＤ法で作製する場合、次のような問題点があった。即ち、原料である化合物が熱的安定性、および水分に対する安定性に乏しく、成膜中、気化器内部で分解が加速度的に起こり、膜を堆積する成膜室において分解した配位子に起因する有機物のみが気化し原料錯体の気化を妨げ、不均一で安定しない原料の供給が行われていた。このため従来のＴｉＮ膜形成用の原料では、所望のＴｉＮ膜を高純度で作製することは困難であった。 However, when the TiN film is formed by the MOCVD method using the above raw materials, there are the following problems. That is, the compound as a raw material has poor thermal stability and moisture stability, and during film formation, decomposition occurs at an accelerated rate inside the vaporizer, resulting from the decomposition of the ligand in the film formation chamber where the film is deposited. As a result, only the organic substances that vaporize vaporize and hinder the vaporization of the raw material complex, and a non-uniform and unstable raw material was supplied. For this reason, it has been difficult to produce a desired TiN film with high purity by using conventional materials for forming a TiN film.
そこで本発明の目的は、ＭＯＣＶＤ法により均一で安定した気化を行うことができ所望のチタン含有薄膜を得ることができるチタン含有薄膜の製造方法、及びその方法で得られたチタン含有薄膜を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing a titanium-containing thin film capable of obtaining a desired titanium-containing thin film by performing uniform and stable vaporization by MOCVD, and a titanium-containing thin film obtained by the method. There is.
本発明者らは上述のような現状に鑑み、鋭意検討を重ねた結果、特定のチタン錯体を原料に用いて、ＭＯＣＶＤ法により薄膜を製造することにより、不都合が生じることなく所望のチタン含有薄膜を得られることを見出し、本発明に到達した。 As a result of intensive studies in view of the above-mentioned present situation, the present inventors have produced a desired titanium-containing thin film without causing any inconvenience by producing a thin film by MOCVD using a specific titanium complex as a raw material. The present invention has been reached.
すなわち、本発明は、式（１） That is, the present invention provides the formula (1)
本発明では、上記式（１）で示されるチタン錯体を原料とすることを特徴とする。このチタン錯体は、均一で安定に気化することが好ましいという点を考慮すると、前述の式（１）で表されるもの中でも、好ましくはｋ＝１、ｍ＝１、ｎ＝３であり、Ｒ１及びＲ２がメチル基、Ｒ３がメチル基、エチル基、イソプロピル基、ｔ−ブチル基、トリメチルシリル基、又はｎ−ブチル基である。 In the present invention, the titanium complex represented by the above formula (1) is used as a raw material. In consideration of the fact that this titanium complex is preferably vaporized uniformly and stably, among those represented by the above formula (1), preferably k = 1, m = 1, n = 3, and R 1 and R 2 are a methyl group, R 3 is a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a trimethylsilyl group, or an n-butyl group.
より好ましい具体例としてはｋ＝１、ｍ＝１、ｎ＝３、Ｒ１及びＲ２がメチル基であり、Ｒ３がメチル基［（ＣＨ３Ｃ５Ｈ４）Ｔｉ（Ｎ（ＣＨ３）２）３（以下、ＭｅＣｐＴｉ（ＮＭｅ２）３という。）］、Ｒ３がエチル基［（ＣＨ３ＣＨ２Ｃ５Ｈ４）Ｔｉ（Ｎ（ＣＨ３）２）３（以下、ＥｔＣｐＴｉ（ＮＭｅ２）３という。）］、Ｒ３がイソプロピル基［（ｉｓｏ−Ｃ３Ｈ７Ｃ５Ｈ４）Ｔｉ（Ｎ（ＣＨ３）２）３（以下、ｉｓｏ−ＰｒＣｐＴｉ（ＮＭｅ２）３という。）］、Ｒ３がｔ−ブチル基［（ｔ−Ｃ４Ｈ９Ｃ５Ｈ４）Ｔｉ（Ｎ（ＣＨ３）２）３（以下、ｔ−ＢｕＣｐＴｉ（ＮＭｅ２）３という。）］、Ｒ３がトリメチルシリル基［（ＣＨ３）３ＳｉＣ５Ｈ４）Ｔｉ（Ｎ（ＣＨ３）２）３（以下、Ｍｅ３ＳｉＣｐＴｉ（ＮＭｅ２）３という。）］、またはＲ３がｎ−ブチル基［（Ｃ４Ｈ９Ｃ５Ｈ４）Ｔｉ（Ｎ（ＣＨ３）２）３（以下、ｎ−ＢｕＣｐＴｉ（ＮＭｅ２）３という。）］である。
As more preferred specific examples, k = 1, m = 1, n = 3, R 1 and R 2 are methyl groups, and R 3 is a methyl group [(CH 3 C 5 H 4 ) Ti (N (CH 3 ) 2 ) 3 (hereinafter referred to as MeCpTi (NMe 2 ) 3 )], R 3 is an ethyl group [(CH 3 CH 2 C 5 H 4 ) Ti (N (CH 3 ) 2 ) 3 (hereinafter referred to as EtCpTi (NMe 2). ) 3 that.)], R 3 is an isopropyl group [(iso-C 3 H 7 C 5 H 4) Ti (N (CH 3) 2) 3 ( hereinafter, iso-PrCpTi (NMe 2) 3 that.) , R 3 is a t-butyl group [(t-C 4 H 9 C 5 H 4 ) Ti (N (CH 3 ) 2 ) 3 (hereinafter referred to as t-BuCpTi (NMe 2 ) 3 )], R 3 is. trimethylsilyl group [(CH 3) 3 SiC 5 H 4) Ti (N (
本発明で用いられるＭＯＣＶＤ法としては特に限定はなく、また式（１）で表されるチタン錯体を供給する方法としては、例えばバブリング法、ベーキングユニット法、溶液気化法などがあげられるが、溶液気化法は成膜室の直前で原料を気化させて供給するため原料の熱変性が生じにくく、好ましい方法である。式（１）で表されるチタン錯体を有機溶媒に溶解して用いる場合、その有機溶媒としては、式（１）で表されるチタン錯体と反応しないものであれば特に限定されないが、例えばヘキサン、シクロヘキサン、ヘプタン、オクタン、トルエン、キシレン等の炭化水素類が好ましい。 The MOCVD method used in the present invention is not particularly limited, and examples of the method for supplying the titanium complex represented by the formula (1) include a bubbling method, a baking unit method, and a solution vaporization method. The vaporization method is a preferable method because the raw material is vaporized and supplied immediately before the film formation chamber, so that the thermal denaturation of the raw material hardly occurs. When the titanium complex represented by the formula (1) is used by dissolving in an organic solvent, the organic solvent is not particularly limited as long as it does not react with the titanium complex represented by the formula (1). Hydrocarbons such as cyclohexane, heptane, octane, toluene and xylene are preferred.
一例として、各原料を瞬時に気化させ成膜室に送る溶液気化ＣＶＤ法について説明すると、ＭＯＣＶＤ装置は例えば図１に示すものが使用できる。ここでは成膜室４と蒸気発生装置３を備え、成膜室内部にはヒーター６を設け、そのヒーター上に基板５を保持する。この成膜室内部は真空引きされる。成膜室にはＮ含有ガス９の導入管、Ｓｉ含有ガス１０の導入管が接続される。原料容器１に貯蔵されているチタン錯体は気化器２に搬送され、気化され蒸気となり、気化器２へ導入されたＮ２、Ｈｅ、Ａｒ等の不活性ガスからなるキャリアガス８により成膜室４内の基板５上に供給され、基板５上で分解されることによりチタン含有薄膜が製造される。
As an example, a description will be given of a solution vaporization CVD method in which each raw material is instantly vaporized and sent to a film forming chamber. For example, the MOCVD apparatus shown in FIG. 1 can be used. Here, a
基板上での分解は熱により行われるばかりでなく、プラズマ、光等を併用しても良い。また、モノシラン、ジシラン、ジクロロシラン、トリクロロシラン、テトラクロロシラン等のＳｉ含有ガスや、アンモニア、メチルヒドラジン、ジメチルヒドラジン、エチルヒドラジン、ジエチルヒドラジン、ブチルヒドラジン、フェニルヒドラジン、アジ化エチル、アジ化ブチル、アジ化フェニル等のＮ含有ガスを供給して成膜することにより、金属チタンだけでなく、ＴｉＮ、珪化チタン、珪窒化チタン等のチタン含有薄膜を製造することができる。 The decomposition on the substrate is not only performed by heat, but plasma, light, or the like may be used in combination. Also, Si-containing gas such as monosilane, disilane, dichlorosilane, trichlorosilane, tetrachlorosilane, ammonia, methyl hydrazine, dimethyl hydrazine, ethyl hydrazine, diethyl hydrazine, butyl hydrazine, phenyl hydrazine, ethyl azide, butyl azide, azide By forming a film by supplying an N-containing gas such as phenyl phosphide, it is possible to produce not only metallic titanium but also a titanium-containing thin film such as TiN, titanium silicide, and titanium silicate nitride.
このチタン含有薄膜は、例えばシリコン基板表面のＳｉＯ２膜上にＭＯＣＶＤ法により形成され、このチタン含有薄膜の上に更にＡｌやＣｕなどの薄膜を形成することができる。なお、本発明において基板を用いる場合はその種類は特に限定されるものではない。 This titanium-containing thin film is formed, for example, on the SiO 2 film on the surface of the silicon substrate by MOCVD, and a thin film such as Al or Cu can be further formed on the titanium-containing thin film. In addition, when using a board | substrate in this invention, the kind is not specifically limited.
以上述べたように、本発明の上記式（１）で示されるチタン錯体を原料を原料としてＭＯＣＶＤ法を行うことにより、安定した成膜が可能となり、所望のチタン含有薄膜を得ることができる。 As described above, by performing the MOCVD method using the titanium complex represented by the above formula (1) of the present invention as a raw material, stable film formation is possible, and a desired titanium-containing thin film can be obtained.
次に本発明を実施例を用いて更に詳しく説明する。しかし本発明はこれら実施例のみに限定されるものではない。 Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
＜実施例１＞
ＥｔＣｐＴｉ（ＮＭｅ２）３について、高純度Ａｒ ４００ｃｃ／分、１０℃／分の条件において、熱重量減少分析測定を行った。また比較のためにシクロペンタジエニルトリス（ジメチルアミノ）チタン（以下、ＣｐＴｉ（ＮＭｅ２）３という。）、ＴＤＭＡＴ、ＴＤＥＡＴについても、同様に熱重量減少分析測定を行った。結果を図２に示す。
<Example 1>
EtCpTi (NMe 2 ) 3 was subjected to thermogravimetry analysis measurement under conditions of high purity Ar 400 cc / min and 10 ° C./min. For comparison, cyclopentadienyltris (dimethylamino) titanium (hereinafter referred to as CpTi (NMe 2 ) 3 ), TDMAT, and TDEAT were similarly subjected to thermogravimetric reduction analysis measurement. The results are shown in FIG.
ＥｔＣｐＴｉ（ＮＭｅ２）３は、均一に気化し、最終的に８０％強重量減少したことからＣＶＤ用材料として適したものであるといえる。一方、ＣｐＴｉ（ＮＭｅ２）３は気化特性が悪く、不均一に気化し最終的に４０％強しか重量減少しないことから、ＣＶＤ用材料としては不適切であった。また、ＴＤＭＡＴ、ＴＤＥＡＴの場合、４０〜６０℃付近において直線的な重量減少があり、低温において、熱分解又は高純度Ａｒ中に残存するわずかな水との反応による分解が起こっていることが示唆された。 EtCpTi (NMe 2 ) 3 can be said to be suitable as a material for CVD because it is vaporized uniformly and finally reduced in weight by 80%. On the other hand, CpTi (NMe 2 ) 3 is not suitable as a material for CVD because it has poor vaporization characteristics and is vaporized unevenly, resulting in a weight loss of only 40%. In addition, in the case of TDMAT and TDEAT, there is a linear weight decrease in the vicinity of 40 to 60 ° C., suggesting that thermal decomposition or decomposition due to reaction with slight water remaining in high-purity Ar occurs at low temperatures. It was done.
＜実施例２＞
ＭｅＣｐＴｉ（ＮＭｅ２）３をオクタンに０．１ｍｏｌ／ｌで溶かしたものを用いて、ＭＯＣＶＤ法により以下のようにＴｉＮ膜を作製した。まず基板として、基板表面にＳｉＯ２膜（厚さ４０００Å）が熱酸化により形成されたシリコン基板を用意した。用意した基板を装置の成膜室に設置し、基板温度を３００℃とした。気化温度を１２０℃、圧力を１Ｔｏｒｒに設定した。キャリアガスとしてＡｒガスを用い、その流量を１００ｃｃｍとした。また、反応ガスとしてＮＨ３ガスを用い、５００ｃｃｍの流量とした。前述の錯体溶液
を０．０１ｃｃ／分の割合で３０分間供給した。ＴｉＮ膜が得られたことをＸ線回折により確認した。膜厚はＳＥＭにより測定したところ約４０ｎｍであった。
<Example 2>
A TiN film was prepared by MOCVD as follows using MeCpTi (NMe 2 ) 3 dissolved in octane at 0.1 mol / l. First, a silicon substrate having a SiO 2 film (thickness: 4000 mm) formed on the substrate surface by thermal oxidation was prepared as a substrate. The prepared substrate was placed in the film forming chamber of the apparatus, and the substrate temperature was set to 300 ° C. The vaporization temperature was set to 120 ° C. and the pressure was set to 1 Torr. Ar gas was used as a carrier gas, and the flow rate was set to 100 ccm. Further, NH 3 gas was used as the reaction gas, and the flow rate was 500 ccm. The aforementioned complex solution was supplied at a rate of 0.01 cc / min for 30 minutes. It was confirmed by X-ray diffraction that a TiN film was obtained. The film thickness was about 40 nm as measured by SEM.
＜実施例３＞
ＭｅＣｐＴｉ（ＮＭｅ２）３溶液の代わりに、液体のＥｔＣｐＴｉ（ＮＭｅ２）３をそのまま０．００３ｃｃ／分の割合で供給したこと以外は、実施例２と同様な条件でＭＯＣＶＤ法によりＴｉＮ膜を作製した。ＴｉＮ膜が得られたことをＸ線回折により確認した。膜厚はＳＥＭにより測定したところ約５０ｎｍであった。
<Example 3>
A TiN film was formed by MOCVD under the same conditions as in Example 2 except that liquid EtCpTi (NMe 2 ) 3 was supplied as it was at a rate of 0.003 cc / min instead of the MeCpTi (NMe 2 ) 3 solution. did. It was confirmed by X-ray diffraction that a TiN film was obtained. The film thickness was about 50 nm as measured by SEM.
＜実施例４＞
ｉｓｏ−ＰｒＣｐＴｉ（ＮＭｅ２）３をオクタンに０．１ｍｏｌ／ｌで溶かしたものを用いた以外は、実施例２と同様な条件でＭＯＣＶＤ法によりＴｉＮ膜を作製した。ＴｉＮ膜が得られたことをＸ線回折により確認した。膜厚はＳＥＭにより測定したところ約４０ｎｍであった。
<Example 4>
A TiN film was produced by MOCVD under the same conditions as in Example 2 except that iso-PrCpTi (NMe 2 ) 3 dissolved in octane at 0.1 mol / l was used. It was confirmed by X-ray diffraction that a TiN film was obtained. The film thickness was about 40 nm as measured by SEM.
＜実施例５＞
ｔ−ＢｕＣｐＴｉ（ＮＭｅ２）３をオクタンに０．１ｍｏｌ／ｌで溶かしたものを用いて、実施例２と同様な条件でＭＯＣＶＤ法によりＴｉＮ膜を作製した。ＴｉＮ膜が得られたことをＸ線回折により確認した。膜厚はＳＥＭにより測定したところ約３０ｎｍであった。
<Example 5>
A TiN film was prepared by MOCVD under the same conditions as in Example 2 using t-BuCpTi (NMe 2 ) 3 dissolved in octane at 0.1 mol / l. It was confirmed by X-ray diffraction that a TiN film was obtained. The film thickness was about 30 nm as measured by SEM.
＜実施例６＞
Ｍｅ３ＳｉＣｐＴｉ（ＮＭｅ２）３をオクタンに０．１ｍｏｌ／ｌで溶かしたものを用いて、実施例２と同様な条件でＭＯＣＶＤ法によりＴｉＮ膜を作製した。ＴｉＮ膜が得られたことをＸ線回折により確認した。膜厚はＳＥＭにより測定したところ約３０ｎｍであった。
<Example 6>
A TiN film was prepared by MOCVD under the same conditions as in Example 2 using Me 3 SiCpTi (NMe 2 ) 3 dissolved in octane at 0.1 mol / l. It was confirmed by X-ray diffraction that a TiN film was obtained. The film thickness was about 30 nm as measured by SEM.
＜実施例７＞
液体のｎ−ＢｕＣｐＴｉ（ＮＭｅ２）３をそのまま用いて、実施例３と同様な条件でＭＯＣＶＤ法によりＴｉＮ膜を作製した。ＴｉＮ膜が得られたことをＸ線回折により確認した。膜厚はＳＥＭにより測定したところ約３０ｎｍであった。
<Example 7>
Using a liquid n-BuCpTi (NMe 2 ) 3 as it was, a TiN film was produced by MOCVD under the same conditions as in Example 3. It was confirmed by X-ray diffraction that a TiN film was obtained. The film thickness was about 30 nm as measured by SEM.
１．原料容器
２．気化器
３．蒸気発生装置
４．成膜室
５．基板
６．ヒーター
７．真空ポンプ
８．キャリアガス
９．Ｎ含有ガス
１０．Ｓｉ含有ガス
1.
Claims (3)
A titanium-containing thin film produced by the method according to claim 1 or 2.
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