Semiconductor device manufacturing: process – Coating with electrically or thermally conductive material – To form ohmic contact to semiconductive material
Reexamination Certificate
2002-03-19
2004-01-27
Whitehead, Jr., Carl (Department: 2813)
Semiconductor device manufacturing: process
Coating with electrically or thermally conductive material
To form ohmic contact to semiconductive material
C438S003000, C438S575000, C438S580000, C438S650000, C438S240000, C438S104000
Reexamination Certificate
active
06683001
ABSTRACT:
RELATED APPLICATION
This application relies for priority upon Korean Patent Application No. 2001-18961, filed on Apr. 10, 2001, the contents of which are herein incorporated by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates to a method for manufacturing a semiconductor device having a metal layer.
BACKGROUND OF THE INVENTION
In integrated circuits, such as semiconductor devices, insulating layers and conductive layers are arranged in vertical and horizontal directions by a predetermined rule, and devices such as transistors, capacitors, interconnection layers, and plugs for connecting to interconnection layers, are formed by such arrangements. However, when semiconductor devices are formed on an upper portion of a first already-formed semiconductor device, the electrical characteristics of the firstly formed device may be changed and degraded by the later formed semiconductor device.
An example of variation in the characteristics of a first semiconductor device resulting from a subsequent process in the formation of a second semiconductor device can be found in a capacitor. In general, when manufacturing a capacitor, a lower electrode is first formed of a conductive material on a substrate, and a dielectric layer is formed on an upper portion of the lower electrode. Before forming an upper electrode on the dielectric layer, the dielectric layer is crystallized by annealing at about 700° C. to improve the dielectric property of the capacitor. Next, the upper electrode is formed of a conductive material on the crystallized dielectric layer. In order to reduce leakage current caused by crystallization annealing at 700° C., curing is performed at about 400° C. in an oxygen atmosphere.
In a conventional metal-insulator-semiconductor (MIS) capacitor, polysilicon is used as a conductive material for a lower electrode and metal is used as a conductive material for an upper electrode. However, in more highly integrated semiconductor devices, the use of metal-insulator-metal (MIM) capacitors, in which lower and upper electrodes are formed of metal, is more common. Recently, noble metals such as platinum (Pt), ruthenium (Ru), iridium (Ir), rhodium (Rh), and osmium (Os), which do not react with the dielectric layer and have a high work function value, are used as upper and/or lower electrodes of capacitors.
Among the above metals, there is little reaction of Pt with oxygen at an interface with a dielectric layer of the oxide family, so that the surface of the Pt does not significantly oxidize even in a high temperature heating process in an oxygen atmosphere where crystallization annealing and curing are performed to improve the dielectric property. However, the surface of metals such as Ru, Ir, palladium (Pd), Rh, or Os, can be easily oxidized in a crystallization annealing and/or curing process, which may cause the metal oxide surface to have an expanded volume, increased surface roughness, and more varied surface morphology. These effects can be particularly significant when using a curing process to improve an interfacial property between an upper electrode and a dielectric layer at over 400° C.
In more highly integrated semiconductor devices, electrodes of a capacitor are typically thinner, and metal oxide is typically formed at lower temperatures. For example, a photo of a state in which a ruthenium (Ru) layer having a thickness of 1000 Å is heated (cured) in an oxygen atmosphere at 400° C., is shown in
FIG. 1A
, and a photo of a state in which a Ru layer having a thickness of 300 Å is heated (cured) at the same temperature, is shown in FIG.
1
B. As shown in
FIGS. 1A and 1B
, the surface roughness of the thinner layer increased more, and its surface morphology became more varied, compared to the thicker layer. As shown in
FIG. 2
, swells
2
of ruthenium oxide (RuO
2
) are formed on the surface of an Ru layer
1
by thermal oxidation. The presence of the swells
2
(
FIG. 2
) and as shown in
FIG. 1A
renders the surface of Ru layer
1
not substantially flat which, when used within a capacitor, can result in an increase in the resistance and leakage current of the capacitor.
Thus, in order to reduce leakage current and resistance when using metals such as Ru, Ir, Pd, Rh, or Os to form electrodes of a capacitor, a technology for suppressing degradation of the surface of the metals is required.
SUMMARY OF THE INVENTION
According to embodiments of the present invention, methods of manufacturing a semiconductor device having a metal layer are provided which may limit changes to the surface roughness of metal layer during a curing process for the device. According to some embodiments, a metal layer is formed on a semiconductor substrate. The metal layer is pretreated by low temperature-oxidation at a first temperature, for example, about 150° C., so that an upper surface of the metal layer is changed into a mixed phase of metal and oxygen. The metal layer is then heated at a second temperature higher than the first temperature, for example, about 400° C., in an oxygen atmosphere.
In further embodiments, the metal layer is sufficiently oxidized during the low temperature oxidation pretreatment so that it is substantially resistant to further oxidation during a higher temperature heating, such as during a curing process to change a predetermined interfacial property between the metal layer and another semiconductor layer. The pretreatment is performed at a temperature and for a time duration for which the surface roughness of the metal layer is not substantially changed but for which it is rendered substantially resistant to further oxidation. By rendering the metal layer substantially resistant to further oxidation while not substantially changing its surface roughness, the surface roughness of the metal layer will be substantially resistant to change from oxidation during a subsequent higher temperature heating process.
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Chung Eun-ae
Hwang Doo-sup
Yoo Cha-young
Hogans David L.
Jr. Carl Whitehead
Myers Bigel & Sibley & Sajovec
Samsung Electronic Co. Ltd.
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