A claim of priority under 35 U.S.C § 119 is made to Korean Patent Application No. 10-2008-0037142, filed Apr. 22, 2008, and to Korean Patent Application No. 10-2008-0092855, filed Sep. 22, 2008. The entirety of both priority applications is herein incorporated by reference.
The present invention generally relates to the formation of a chalcogenide film which includes, for example, antimony (Sb), germanium (Ge), and/or tellurium (Te).
Chalcogenide films are utilized, for example, as the phase-change material layer of phase-change memory devices. Each unit memory cell of a phase-change memory device is programmable in at least two material phase states, i.e., a crystalline state which exhibits a relatively low resistance and an amorphous state which exhibits a relatively high resistance. Programming is achieved by subjecting the chalcogenide film of the memory cell to different thermal conditions, typically induced by joule heating and cooling.
As mentioned above, the present invention generally relates to the formation of a chalcogenide film. For example, in one aspect of the invention, a method of forming a chalcogenide film is provided which includes forming a germanium film on a substrate by exposing the substrate to a germanium source and a first antimony source, and growing a polynary film from the germanium film by exposing the germanium film to at least one of a tellurium source and a second antimony source.
The present invention also generally relates to the fabrication of a memory device. For example, in another aspect of the invention, a method of fabricating a memory device is provided which includes forming an insulating layer which includes an opening that exposes a bottom electrode, forming a chalcogenide pattern which fills the opening, and forming a top electrode on the chalcogenide pattern. The formation of the chalcogenide pattern includes forming a germanium film within the opening by exposing the opening to a germanium source and a first antimony source, and growing a polynary film from the germanium film by exposing the germanium film to at least one of a tellurium source and a second antimony source.
The above and other aspects and features of the present invention will become readily apparent from the detailed description that follows, with reference to the accompanying drawings, in which:
The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. This invention, however, may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the thicknesses of layers and regions are exaggerated for clarity.
It will be understood that when an element or layer is referred to as being “on,” “connected to” or “coupled to” another element or layer, it can be directly on, connected or coupled to the other element or layer or intervening elements or layers may be present. In contrast, when an element is referred to as being “directly on,” “directly connected to” or “directly coupled to” another element or layer, there are no intervening elements or layers present. Like numerals refer to like elements throughout. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
A method of forming a chalcogenide thin film according to an exemplary and non-limiting embodiment of the present invention will now be described with reference to
Referring to
The germanium source may, for example, be one or more selected from the group consisting of (CH3)4Ge, (C2H5)4Ge, (n-C4H9)4Ge, (i-C4H9)4Ge, (C6H5)4Ge, (CH2=CH)4Ge, (CH2CH=CH2)4Ge, (CF2=CF)4Ge, (C6H5CH2CH2CH2)4Ge, (CH3)3(C6H5)Ge, (CH3)3(C6H5CH2)Ge, (CH3)2(C2H5)2Ge, (CH3)2(C6H6)2Ge, CH3(C2H5)3Ge, (CH3)3(CH=CH2)Ge, (CH3)3(CH2CH=CH2)Ge, (C2H5)3(CH2CH=CH2)Ge, (C2H5)3(C5H5)Ge, (CH3)3GeH, (C2H5)3GeH, (C3H7)3GeH, Ge(N(CH3)2)4, Ge(N(CH3)(C2H5))4, Ge(N(C2H5)2)4, Ge(N(i-C3H7)2)4, and Ge[N(Si(CH3)3)2]4.
The first antimony source may, for example, be one or more selected from the group consisting of Sb(CH3)3, Sb(C2H5)3, Sb(i-C3H7)3, Sb(n-C3H7)3, Sb(i-C4H9)3, Sb(t-C4H9)3, Sb(N(CH3)2)3. Sb(N(CH3)(C2H5))3, Sb(N(C2H5)2)3, Sb(N(i-C3H7)2)3, and Sb[N(Si(CH3)3)2]3.
The germanium thin film 220 may, for example, be formed by metal organic chemical vapor deposition (MOCVD). The germanium source and the first antimony source may be simultaneously supplied into an atmosphere containing the substrate 210.
The germanium thin film 220 may be formed to selectively include germanium, while does not include antimony. In other words, the germanium thin film 220 may be an antimony-free (Sb-free) unary thin film. The first antimony source does not constitute the germanium thin film 220, but may assist deposition of the germanium thin film 220. Decomposition of the germanium source is an exothermic reaction, and that of the first antimony source is an endothermic reaction. Thus, interaction between decompositions of the sources may be allowed to expedite the decomposition of the germanium source and the deposition of the germanium thin film 220.
The deposition rate of the germanium thin film 220 may be controlled by controlling a flow rate of the germanium source and the first antimony source. Since the first antimony source serves to expedite growth of the germanium thin film 220, the deposition rate of the germanium thin film 220 may become higher as an amount of the first antimony source is increased. However, if the amount of the first antimony source is greater than that of the germanium source, antimony particles may be generated by aggregation of antimony atoms. The antimony particles may remain on the germanium thin film 220 to make a surface of the germanium thin film 220 uneven. That is, the germanium thin film 220 may be degraded. Therefore, the amount of the first antimony source provided may be smaller than that of the germanium source.
Referring to
The binary thin film 230 may be formed by means of, for example, metal organic chemical vapor deposition (MOCVD). Providing the tellurium source may allow the unary thin film 220 of germanium to grow into a binary thin film 230 of germanium and tellurium. That is, the binary thin film 230 may include germanium and tellurium which constitute a single layer, not separated layers.
Referring to
The ternary thin film 240 may be formed by means of, for example, metal organic chemical vapor deposition (MOCVD). Providing the second antimony source may allow the binary thin film 230 to grow into a ternary thin film 240 of germanium, tellurium, and antimony. That is, the ternary thin film 240 may include germanium, tellurium, and antimony which constitute a single layer, not separated layers.
A deposition apparatus 300 that may be utilized to form a chalcogenide thin film according to an exemplary embodiment of the present invention will now be described below in detail with reference to
The deposition apparatus 300 of this example includes a carrier supply unit 310 configured to supply carrier material and a bubbler 335 in which source materials are contained. The carrier supply unit 310 and the bubbler 335 are connected to each other by supply pipes 315, and the bubbler 335 is connected to a cooling system 330. A plurality of bubblers, corresponding in number to the number of the source materials, may be provided between the carrier supply unit 310 and a chamber 340. A flow rate of the source materials is controlled by controlling a temperature of the bubbler 335 or the amount of the carrier material. The source materials are carried into the chamber 340 by the carrier material.
The supply pipes 315 are connected to the chamber 340 where a thin film is formed. The source material is supplied into the chamber 340 through the supply pipes 315 without being mixed or after being mixed. A valve or the like may be mounted on the supply pipes 315 to control a flow rate of gas supplied into the chamber 340.
The chamber 340 includes a shower head 342, a susceptor 344, and a heater 346 therein. The shower head 342 is disposed at an upper portion within the chamber 340, and the susceptor 344 is disposed at a lower portion within the chamber 340 to face the shower head 342. The source materials flowing through the respective supply pipes 315 may meet one another before arriving at the shower head 342. The source materials supplied into the chamber 340 are sprayed towards the susceptor 344 which is installed at the center within the chamber 340, on which a substrate is loaded. The heater 346 is installed in a base for supporting the susceptor 344 and increases a temperature of a substrate (or wafer) loaded on the susceptor 344. The chamber 340 may further include an outlet (not shown) formed to exhaust gases generated or used inside the chamber 340.
The deposition apparatus 300 of this example further includes a pressure gage 350 configured to check an internal pressure of the chamber 340, a thermometer 352 configured to measure a temperature of the heater 346, a controller 354 configured to control the temperature of the heater 346, and a power supply unit 356 configured to supply a power to the heater 346.
The deposition apparatus 300 of this example further includes a reactive gas supply unit 320 configured to supply other reactive gases.
A method of forming chalcogenide thin films according to an exemplary embodiment of the present invention and characteristics of the thin films formed thereby will now be described below in detail.
A germanium thin film may be formed on a substrate. There may be a conductive layer (e.g., titanium aluminum nitride (TiAIN) layer) on the substrate (e.g., silicon wafer). The germanium thin film may, for example, be formed by means of the deposition apparatus 300 described in
Characteristics of a germanium thin film according to an exemplary embodiment of the present invention will now be described with reference to
X-ray diffraction (XRD) characteristics of germanium thin films formed based on temperatures of the bubbler 335 including Sb(iPr)3 will be described with reference to
Referring to
Although not illustrated, if only a germanium source (e.g., Ge(ally)4) is supplied without supplying the first antimony source (e.g., Sb(iPr)3), a germanium thin film may not be formed.
The above-described germanium thin film may grow into a binary thin film of germanium and tellurium. The binary thin film may be formed using a tellurium source which is supplied into the chamber 340. The tellurium source may, for example, be one selected from the group consisting of Te(CH3)2, Te(C2H5)2, Te(n-C3H7)2, Te(i-C3H7)2, Te(t-C4H9)2, Te(i-C4H9)2, Te(CH2=CH)2, Te(CH2CH=CH2)2, and Te[N(Si(CH3)3)2]2.
Characteristics of the binary thin film will be described with reference to
X-ray diffraction (XRD) characteristics of the binary thin film will be described with reference to
Referring to
The binary thin film formed by means of the above-described method may grow into a ternary thin film of germanium, tellurium, and antimony. The ternary thin film may be formed using a second antimony source. The second antimony source may be supplied into the chamber 340. The second antimony source may include one selected from the group consisting of Sb(CH3)3, Sb(C2H5)3, Sb(i-C3H7)3, Sb(n-C3H7)3, Sb(i-C4H9)3, Sb(t-C4H9)3, Sb(N(CH3)2)3, Sb(N(CH3)(C2H5))3, Sb(N(C2H5)2)3. Sb(N(i-C3H7)2)3, and Sb[N(Si(CH3)3)2]3.
Characteristics of the ternary thin film will be described with reference to
Referring to
A method of fabricating a memory device including a chalcogenide thin film according to an exemplary embodiment of the present invention will now be described below in detail with reference to the cross-sectional examples of
Referring to
The bottom electrode 435 may, for example, be formed by means of stacking using physical vapor deposition (PVD) or chemical vapor deposition (CVD) and a patterning processes.
A second interlayer dielectric 425 is formed on the bottom electrode 435. The second interlayer dielectric 425 is patterned to form an opening 428 to expose a portion of the bottom electrode 425 within the second interlayer dielectric 425.
Referring to
The phase-change material 440 is formed in the opening 428 and on the second interlayer dielectric 425. In this example, the opening 428 is filled with the phase-change material layer 440.
Referring to
The conductive layer 450 may be formed of the same material as the bottom electrode 435 or of a material which is different from that of the bottom electrode 435.
Still referring to
Referring to
Referring to
A method of fabricating a memory device including a chalcogenide thin film according to another exemplary embodiment of the present invention will now be described below in detail with reference to the cross-sectional examples of
Referring to
Referring to
As described above, by exposing a substrate to a germanium source and an antimony source, a germanium thin film that is substantially free of antimony can be formed on the substrate. Further, by then sequentially supplying a tellurium source and an antimony source, a polynary thin film can be formed which exhibits favorable properties in which three kinds of atoms can coexist in a single layer according to a desired composition ratio. A phase-change material layer having favorable step coverage characteristics and a uniform composition ratio can thus be formed.
Although the present invention has been described in connection with the exemplary embodiment of the present invention illustrated in the accompanying drawings, it is not limited thereto. It will be apparent to those skilled in the art that various substitutions, modifications and changes may be made without departing from the scope and spirit of the invention.
Number | Date | Country | Kind |
---|---|---|---|
2008-37142 | Apr 2008 | KR | national |
2008-92855 | Sep 2008 | KR | national |