JP2629939B2 - Diamond film manufacturing method - Google Patents
Diamond film manufacturing methodInfo
- Publication number
- JP2629939B2 JP2629939B2 JP2685589A JP2685589A JP2629939B2 JP 2629939 B2 JP2629939 B2 JP 2629939B2 JP 2685589 A JP2685589 A JP 2685589A JP 2685589 A JP2685589 A JP 2685589A JP 2629939 B2 JP2629939 B2 JP 2629939B2
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- processed
- diamond film
- intermediate layer
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910003460 diamond Inorganic materials 0.000 title claims description 55
- 239000010432 diamond Substances 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 description 14
- 239000000470 constituent Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910039444 MoC Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- KEUKAQNPUBYCIC-UHFFFAOYSA-N ethaneperoxoic acid;hydrogen peroxide Chemical compound OO.CC(=O)OO KEUKAQNPUBYCIC-UHFFFAOYSA-N 0.000 description 2
- -1 for example Natural products 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- CNEOGBIICRAWOH-UHFFFAOYSA-N methane;molybdenum Chemical compound C.[Mo] CNEOGBIICRAWOH-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】 〔概要〕 被処理物体上へのダイヤモンド膜の製造方法に関し、 被処理物体との密着力が優れたダイヤモンド膜を製造
することを目的とし、 被処理体上に化学気相成長法により形成するダイヤモ
ンド膜が、同一の製造装置を用い、被処理物体上に、被
処理物体の主な構成元素とダイヤモンドの焼結補助材の
構成元素との混合物からなる第１の中間層と、該第１の
中間層の上に形成され、前記ダイヤモンドの焼結補助材
の構成元素とダイヤモンドの混合物からなる第２の中間
層とを介して形成することでダイヤモンド膜の製造方法
を構成する。DETAILED DESCRIPTION OF THE INVENTION [Summary] The present invention relates to a method for manufacturing a diamond film on an object to be processed, with the object of manufacturing a diamond film having excellent adhesion to the object to be processed, A diamond film formed by a phase growth method is formed on a target object by using the same manufacturing apparatus, and a first intermediate layer composed of a mixture of a main constituent element of the target object and a constituent element of a diamond sintering auxiliary material. A second intermediate layer formed on the first intermediate layer and formed of a mixture of diamond and a constituent element of the diamond sintering aid, thereby forming a diamond film. Configure.
本発明は被処理物体との密着性が優れたダイヤモンド
膜の製造方法に関する。The present invention relates to a method for producing a diamond film having excellent adhesion to an object to be processed.
ダイヤモンドは炭素（Ｃ）の同素体であり、所謂るダ
イヤモンド構造を示し、モース（Mohs）硬度10と大き
く、また熱伝導度は1000W/m kと他の物質に較べて格段
に優れている。Diamond is an allotrope of carbon (C), has a so-called diamond structure, has a large Mohs hardness of 10, and has a thermal conductivity of 1000 W / mk, which is much better than other substances.
そこで、この特性を利用して各種の用途が開発されて
いる。Therefore, various uses have been developed utilizing this characteristic.
すなわち、硬度の高いのを利用してドリルの刃やバイ
トに使用することが考えられており、タングステン・カ
ーバイト（WC）など高硬度な焼結合金からなるこれら工
具の上に被覆して使用することが試みられている。In other words, it is considered to be used for drill blades and cutting tools by using its high hardness. It is used by coating on these tools made of high-hardness sintered alloy such as tungsten carbide (WC). Have been tried to.
また、熱伝導度の高いのを利用してLSIやVLSIなど半
導体集積回路のヒートシンク（Heat−sink）の構成材と
して着目されている。In addition, attention has been paid to constituent materials of heat sinks of semiconductor integrated circuits such as LSIs and VLSIs by utilizing high thermal conductivity.
タングステン・カーバイト（WC）やモリブデン・カー
バイト（MoC）からなる工具の上にダイヤモンド膜を被
覆（Coating）する場合、第４図に示すような化学気相
成長装置（略してCVD装置）を使用して直接に化学気相
成長（略してCVD成長）を行っても熱膨張係数が異なる
ために容易に剥離してしまう。When a diamond film is coated on a tool made of tungsten carbide (WC) or molybdenum carbide (MoC), a chemical vapor deposition apparatus (abbreviated as CVD apparatus) as shown in FIG. 4 is used. Even if it is used and directly subjected to chemical vapor deposition (abbreviated as CVD growth), it is easily peeled off because of its different coefficient of thermal expansion.
いま、簡単に第４図に示すCVD装置の構成と動作を説
明すると次のようになる。Now, the configuration and operation of the CVD apparatus shown in FIG. 4 will be briefly described as follows.
被処理物体（例えば工具など）１は冷却水２によって
水冷された基板ホルダ３の上に載置されている。An object to be processed (for example, a tool) 1 is placed on a substrate holder 3 that has been water-cooled by cooling water 2.
一方、反応室４の上部にはプラズマジェット５を形成
するための陽極６と陰極７があり、この間を通って原料
ガス８が供給され、また金属層の形成を可能とするため
に粉末供給パイプ９が陽極６の先端に開口している。On the other hand, the upper part of the reaction chamber 4 has an anode 6 and a cathode 7 for forming a plasma jet 5, through which raw material gas 8 is supplied, and a powder supply pipe for forming a metal layer. 9 is open at the tip of the anode 6.
また、陽極６と陰極７を繋いで直流電源10があり、反
応室４の下部には排気口11がある。In addition, there is a DC power supply 10 connecting the anode 6 and the cathode 7, and an exhaust port 11 is provided below the reaction chamber 4.
ダイヤモンドのCVD成長を行うには陽極６と陰極７の
間から水素（H2）と炭化水素、例えばメタン（CH4）と
の混合ガスを反応室４の中に供給すると共に、排気系を
動作して排気口11より排気し、反応室４の中を低真空に
保持した状態で陽極陰極間にアーク放電12を生じさせ、
この熱により原料ガス８を分解させてプラズマ化させる
と、炭素プラズマを含むプラズマジェット５は被処理物
体１に当たり、微結晶からなるダイヤモンド膜13が被処
理物体１の上に成長する。To perform CVD growth of diamond, a mixed gas of hydrogen (H 2 ) and a hydrocarbon, for example, methane (CH 4 ) is supplied into the reaction chamber 4 from between the anode 6 and the cathode 7 and the exhaust system is operated. Then, the gas was exhausted from the exhaust port 11, and an arc discharge 12 was generated between the anode and the cathode while the inside of the reaction chamber 4 was maintained at a low vacuum.
When the raw material gas 8 is decomposed into plasma by this heat, the plasma jet 5 containing carbon plasma hits the object 1 to be processed, and a diamond film 13 made of microcrystals grows on the object 1 to be processed.
また、金属とダイヤモンドとの混合膜を成長させるに
は粉末供給パイプ９を通じで金属粉をアーク放電12の中
に供給すればよく、金属膜のみを成長させるには原料ガ
ス８としてH2を用い、粉末供給パイプ９を通じで金属粉
をアーク放電12の中に供給すればよい。In order to grow a mixed film of metal and diamond, metal powder may be supplied into the arc discharge 12 through a powder supply pipe 9. To grow only a metal film, H 2 is used as a source gas 8. The metal powder may be supplied into the arc discharge 12 through the powder supply pipe 9.
このようにすると、被処理物体１の上にダイヤモンド
膜13を成長させることはできるが、熱膨張係数が異なっ
ており（例えば、ダイヤモンドの線膨張係数は0.0132×
10-4K-1であるのに対し、Ｗは0.045×10-4K-1）また、C
VD反応が行われる800℃以上の高温から常温にまで下げ
られるために、ダイヤモンド膜13は容易に被処理物体１
より剥離してしまう。In this way, the diamond film 13 can be grown on the object 1 to be processed, but has a different coefficient of thermal expansion (for example, the coefficient of linear expansion of diamond is 0.0132 ×
10 to -4 for a K -1, W is 0.045 × 10 -4 K -1) Also, C
Since the temperature can be lowered from a high temperature of 800 ° C. or higher at which the VD reaction is performed to a normal temperature, the diamond film 13 can easily be processed.
More peeling.
そのため、従来は例えばWCからなる工具の上にダイヤ
モンド膜を被覆する場合には焼結補助材としてWCの中に
含まれており、密着性を低下させる原因となる元素（例
えばCo）を化学的に除去した後にCVD法によりダイヤモ
ンド膜を成長させたり、或いは機械的な傷を付けた上に
成長させるなどの方法が行われている。Therefore, conventionally, when a diamond film is coated on a tool made of WC, for example, an element (for example, Co) that is included in WC as a sintering aid and that causes a decrease in adhesion is chemically removed. After removal, a diamond film is grown by a CVD method, or a diamond film is grown after being mechanically damaged.
然し、膜厚と共に密着力が低下するために成長膜厚の
限度は数μｍに過ぎず、それでも実用に使用するには密
着性が不足している。However, since the adhesion decreases with the film thickness, the limit of the grown film thickness is only a few μm, and the adhesion is still insufficient for practical use.
発明者はこの問題を解決する方法として第２図に示す
ように被処理物体１の上に熱膨張係数がダイヤモンドに
近いコーティング材料層15を設け、この上にダイヤモン
ド膜13を成長させることを先に提案している（特願昭20
−300154,昭和62年11月30日出願） 然し、実際に適用してみると、工具として使用するに
は密着性が不充分であった。As a method for solving this problem, as shown in FIG. 2, the inventor first provided a coating material layer 15 having a thermal expansion coefficient close to that of diamond on the object 1 to be processed, and grown a diamond film 13 thereon. (Japanese Patent Application No. 20
However, when actually applied, the adhesion was insufficient for use as a tool.
以上記したようにダイヤモンドは硬度が材料中で最も
大きなことから、これを用いてドリルの刃やバイトを形
成することが試みられている。As described above, since diamond has the highest hardness among materials, it has been attempted to form a drill blade or cutting tool using the diamond.
然し、ダイヤモンドをWCなどからなる工具の上に被覆
すると熱膨張係数が異なることから容易に剥離し、実用
化できないことが問題であり、これを解決することが課
題である。However, when diamond is coated on a tool made of WC or the like, the thermal expansion coefficient is different, so that the diamond easily peels off and cannot be put to practical use.
上記の課題を被処理物体上に化学気相成長法により形
成するダイヤモンド膜が、同一の製造装置を用い、被処
理物体上に、被処理物体の主な構成元素とダイヤモンド
の焼結補助材の構成元素との混合物からなる第１の中間
層と、この第１の中間層の上に形成され、ダイヤモンド
の焼結補助材の構成元素とダイヤモンドの混合物からな
る第２の中間層とを介してダイヤモンド膜を形成するこ
とにより解決することができる。The diamond film formed by the chemical vapor deposition method on the object to be processed by the above-mentioned problem is formed on the object to be processed by using the same manufacturing equipment as the main constituent elements of the object to be processed and the sintering aid for diamond. Via a first intermediate layer made of a mixture of constituent elements and a second intermediate layer formed on the first intermediate layer and made of a mixture of a constituent element of a diamond sintering aid and diamond. The problem can be solved by forming a diamond film.
本発明は被処理物体とダイヤモンド膜との密着性を高
める方法として、ダイヤモンド膜を形成するCVD装置を
用い、被処理物体の上に、 第１の中間層／第２の中間層／ダイヤモンド膜と云う
構成をとる二段階の中間層を設けるものである。The present invention uses a CVD apparatus for forming a diamond film as a method for improving the adhesion between the object to be processed and the diamond film, and forms a first intermediate layer / second intermediate layer / diamond film on the object to be processed. A two-stage intermediate layer having such a structure is provided.
第１図は本発明を説明する断面図であって、この図の
場合、被処理物体１はWCやMoCのような焼結体からなっ
ており、この焼結体の中にはコバルト（Co）のような焼
結補助材16が散在している。FIG. 1 is a cross-sectional view for explaining the present invention. In this case, the object to be processed 1 is made of a sintered body such as WC or MoC, and the sintered body includes cobalt (Co). ) Are scattered.
本発明は第１の中間層17を被処理物体１の主な構成材
料であるWCやMoCとダイヤモンドの焼結補助材の構成元
素であるコバルト（Co），鉄（Fe），ニッケル（Ni）の
ような遷移金属との混合物で構成する。In the present invention, the first intermediate layer 17 is formed of cobalt (Co), iron (Fe), nickel (Ni), which are constituent elements of sintering aids of WC, MoC and diamond, which are main constituent materials of the object 1 to be processed. And a mixture with a transition metal.
次に、第２の中間層18はダイヤモンドの焼結補助材の
構成元素とであるコバルト（Co），鉄（Fe），ニッケル
（Ni）のような遷移金属とダイヤモンドとの混合物で構
成する。Next, the second intermediate layer 18 is composed of a mixture of diamond and a transition metal such as cobalt (Co), iron (Fe), nickel (Ni), which is a constituent element of a diamond sintering aid.
そして、この上に、ダイヤモンド膜13を成長させるも
のである。Then, a diamond film 13 is grown thereon.
本発明は、このように二層の中間層を設け、被処理物
体１とダイヤモンド膜13との組成が徐々に変わるよう構
成することにより、100μｍ程度の厚さに形成しても剥
離を生ずることのないダイヤモンド膜13を形成するもの
である。According to the present invention, the two intermediate layers are provided so that the composition of the object 1 to be processed and the diamond film 13 is gradually changed, so that peeling occurs even when the thickness is about 100 μm. This is to form a diamond film 13 having no gap.
被処理物体１としてCoを焼結補助材料とし、組成がWC
−10％Coからなる焼結体を使用し、第１の中間層の構成
材料としてはWCとCoとを使用した。Co is used as a sintering auxiliary material for the object 1 to be processed, and its composition is WC
A sintered body composed of -10% Co was used, and WC and Co were used as constituent materials of the first intermediate layer.
また、第２中間層の構成材料としてはダイヤモンドと
Coとを使用した。Also, diamond is used as a constituent material of the second intermediate layer.
Co and used.
第１の中間層乃至ダイヤモンド膜の成長条件としては
第４図に示したCVD装置を使用し、H2ガスの供給量とし
ては10〜50／分とし、CH2ガスの供給量は0.05〜１
／分とした。The CVD apparatus shown in FIG. 4 was used as the growth conditions for the first intermediate layer to the diamond film, the supply rate of H 2 gas was 10 to 50 / min, and the supply rate of CH 2 gas was 0.05 to 1
/ Min.
また、アーク電流として10〜70Aとし、直流電源の電
圧は50〜150Vの範囲に変えた。The arc current was set to 10 to 70 A, and the voltage of the DC power supply was changed to a range of 50 to 150 V.
また、反応室の真空度は１〜10KPaの範囲に保った。 The degree of vacuum in the reaction chamber was kept in the range of 1 to 10 KPa.
そして、被処理物体上に第１の中間層を成長させる場
合にはH2ガスを原料ガスとして供給し、プラズマジェッ
トを発生させた状態で、粉末供給パイプ９から粒径が１
〜５μｍのWCとCoとを0.01〜0.1cc/時の割合で供給して
プラズマ化させ、20μｍの厚さに混合物を成長させた。When the first intermediate layer is grown on the object to be processed, H 2 gas is supplied as a source gas, and a particle diameter of 1 is supplied from the powder supply pipe 9 while a plasma jet is generated.
WC and Co of ５5 μm were supplied at a rate of 0.01-0.1 cc / hour to form a plasma, and the mixture was grown to a thickness of 20 μm.
次に、原料ガスをH2とCH4の混合ガスに換えると共
に、粉末供給パイプ９から粒径が１〜５μｍのCo粉末を
供給してプラズマジェットを作り、ダイヤモンドとCoの
混合物とからなる第２の中間層を30μｍの厚さに形成し
た。Next, the source gas is changed to a mixed gas of H 2 and CH 4 , and a Co powder having a particle size of 1 to 5 μm is supplied from the powder supply pipe 9 to form a plasma jet, and a plasma jet is formed from a mixture of diamond and Co. The second intermediate layer was formed to a thickness of 30 μm.
第３図は第２の中間層についてのＸ線回折パターンで
あって、ダイヤモンド（略号Ｄ）とCoの回折線が良く現
れており、混合層が成長しているのが判る。FIG. 3 shows an X-ray diffraction pattern of the second intermediate layer, in which diffraction lines of diamond (abbreviation D) and Co are well seen, and it can be seen that a mixed layer is growing.
次に、この上にH2とCH4の混合ガスを原料ガスとして
プラズマジェットを作り、約100μｍの厚さのダイヤモ
ンド膜を成長させた。Next, a plasma jet was formed thereon using a mixed gas of H 2 and CH 4 as a source gas to grow a diamond film having a thickness of about 100 μm.
このようにして形成したダイヤモンド膜の被処理物体
との密着力は強大であって、引張り試験の結果、600Kg/
mm2以上の値を得ることができた。The adhesion of the diamond film thus formed to the object to be processed is strong, and as a result of the tensile test, 600 kg /
mm 2 or more could be obtained.
本発明によれば、被処理物体の上に密着力に優れたダ
イヤモンド膜が被覆できるので、信頼性の高いダイヤモ
ンド工具を提供することができる。According to the present invention, a diamond film having excellent adhesion can be coated on the object to be processed, so that a highly reliable diamond tool can be provided.
第１図は本発明を説明する断面図、 第２図は先に発明者が提案している方法を説明する断面
図、 第３図は第２図の中間層のＸ線回折パターン、 第４図は本発明に使用したCVD装置の断面図、 である。 図において、 １は被処理物体、５はプラズマジェット、 ６は陽極、７は陰極、 ８は原料ガス、９は粉末供給パイプ、 13はダイヤモンド膜、17は第１の中間層、 18は第２の中間層、 である。FIG. 1 is a cross-sectional view for explaining the present invention, FIG. 2 is a cross-sectional view for explaining a method previously proposed by the inventor, FIG. 3 is an X-ray diffraction pattern of the intermediate layer in FIG. FIG. 1 is a sectional view of a CVD apparatus used in the present invention. In the figure, 1 is an object to be processed, 5 is a plasma jet, 6 is an anode, 7 is a cathode, 8 is a source gas, 9 is a powder supply pipe, 13 is a diamond film, 17 is a first intermediate layer, and 18 is a second intermediate layer. The middle layer of.
Claims (1)
するダイヤモンド膜が、同一の製造装置を用い、 被処理物体上に、被処理物体の主な構成元素とダイヤモ
ンドの焼結補助材の構成元素との混合物からなる第１の
中間層と、 該第１の中間層の上に形成され、前記ダイヤモンドの焼
結補助材の構成元素とダイヤモンドの混合物からなる第
２の中間層とを介して形成することを特徴とするダイヤ
モンド膜の製造方法。A diamond film to be formed on an object to be processed by a chemical vapor deposition method using the same manufacturing apparatus, and a main sintering element of the object to be processed and a diamond sintering aid are formed on the object to be processed. And a second intermediate layer formed on the first intermediate layer, the second intermediate layer being composed of a mixture of a component element of the diamond sintering aid and diamond. A method for producing a diamond film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2685589A JP2629939B2 (en) | 1989-02-06 | 1989-02-06 | Diamond film manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2685589A JP2629939B2 (en) | 1989-02-06 | 1989-02-06 | Diamond film manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02208289A JPH02208289A (en) | 1990-08-17 |
| JP2629939B2 true JP2629939B2 (en) | 1997-07-16 |
Family
ID=12204893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2685589A Expired - Fee Related JP2629939B2 (en) | 1989-02-06 | 1989-02-06 | Diamond film manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2629939B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE9004123D0 (en) * | 1990-12-21 | 1990-12-21 | Sandvik Ab | DIAMOND IMPREGNERATED HARD MATERIAL |
-
1989
- 1989-02-06 JP JP2685589A patent/JP2629939B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02208289A (en) | 1990-08-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |
