Dalcin, James R., Grand Island, New York 14072, US; Rogers, Michael C., Lockport, New York 14094, US; Kim, Young-Sig, Chon-Nam, KR; Tressler, Richard E., Boalsburg, Pennsylvania 16827, US; Tworek, John L., West Seneca, New York 14224, US; Viswanathan, Lakshminarayan, East Amherst, New York 14051, US
The present invention relates to a novel phosphorus doping composition
that is used for doping semi-conductor elements at low temperatures. The invention
relates to a novel cerium pentaphosphate doping source for use at low temperatures.
BACKGROUND OF THE INVENTION
Semiconductor elements have various applications and utilities in
the electronic industry and are used as integrated circuits, photodiodes, transistors,
solar batteries, rectifiers, radiation detectors, charge particle detectors and
other applications. Semiconductor elements have been known in the industry for
many years and the term semiconductor element is generally accepted to include
semiconductor devices and parts thereof formed of host substrates comprising elements,
alloys and intermetallic compounds of silicon, germanium, silicon/germanium, arsenic,
gallium, phosphorus, indium and the like. The semiconductor elements can be any
convenient or usable shape but are typically commercially used in the form of circular,
triangular or rectangular wafers or disks.
In order to achieve the various electrical rectification characteristics,
semiconductor elements typically have an active impurity incorporated within the
host substrate. The active impurities are classified as donor impurities or acceptor
impurities; they include phosphorus, arsenic, antimony, silicon, tellurium, tin
and the like and the acceptor impurities include boron, gallium, aluminum, zinc,
cadmium and the like.
The semiconductor element may have a region containing an excess
of donor impurities yielding an excess of free electrons. This region is termed
an impurity doped n-type region. Similarly, a region containing an excess of acceptor
impurities which results in the deficit of electrons is termed impurity doped p-type
region. The boundary between the p-type and n-type regions is termed n-p or p-n
junction. In many applications the uniformity of the impurity distribution within
the p or n-type region is critical to the efficiency of the semiconductor element.
Further, the sharpness of the p-n or n-p junction may be critical to the efficiency
of the semiconductor element. Generally, incorporating various active impurities
in the semiconductor elements have been done during preparation of the host substrate
or by deposition of the host substrate during manufacture.
Solid diffusion sources employing phosphorus have been developed.
U.S.P.N. 3,852,086 discloses a solid diffusion source for phosphorus doping. U.S.P.N.
3,931,056 discloses solid diffusion sources for phosphorus doping containing silicon
and zirconium pyrophosphates. U.S.P.N. 4,526,826 discloses foam semiconductor dopant
carriers for diffusion doping of semiconductors by the vapor phase transport of
an n or p-type dopant, such as phosphorus, arsenic, antimony, boron gallium, aluminum,
zinc, silicon, tellerium, tin and cadmium to the semiconductor host substrate.
U.S.P.N. 4,175,988 discloses polycrystalline ceramics and dopant hosts containing
Solid phosphorus diffusion sources have been disadvantageous because
of the limitation of their temperature ranges.
There have been efforts to make solid phosphorus diffusion sources
for low temperature. U.S.P.N. 4,800,175 discloses phosphorus planar dopant sources
for low temperature applications. However, the sources have had inconsistent diffusion
results at low temperatures and/or were very fragile. A new approach to low temperature
solid phosphorus diffusion sources is necessary.
There is a need for planar dopant sources that will deposit phosphorus
oxides on silicon wafers by vapor transport at low temperatures and provide uniform
doping of silicon at a low sheet resistance for a given temperature.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide a doping composition
and a silicon body being doped by the vapor phase transport of phosphorus oxides
from the source to the silicon body at low temporatures. Another object is to provide
a novel composition containing cerium pentaphosphate for use as a dopant source
at low temperatures. A further object of the invention is to provide a cerium
pentaphosphate dopant source to dope a silicon body uniformly and having controlled
These and other objects will become apparent from the following description
of the present invention.
SYMMARY OF THE INVENTION
The present invention provides a low temperature dopant source for
the vapor phase transport of phosphorus oxides to a silicon body comprising cerium
pentaphosphate composition said composition capable of dissociating and depositing
in the temperature range of about 800°C to about 975°C.
The present invention also provides a process for doping a silicon
a) forming a cerium pentaphosphate dopant source,
b) placing the dopant source with a silicon body to be doped, and
c) maintaining the dopant source and the silicon body at a temperature in the
range of about 800°C to about 975°C to vapor phase transport phosphorus oxides
from the dopant source to diffuse into the silicon body.
DETAILED DESCRIPTION OF THE INVENTION
It has been discovered that cerium pentaphosphate is particularly
suitable as a solid phosphorus diffusion source for doping of semiconductor elements
by vapor phase deposition of phosphorus. The cerium pentaphosphate composition
evolves phosphorus oxides when heated to temperatures in the range of about 800°C
to about 975°C. The reaction is generally described as follows:
CeP&sub5;0&sub1;&sub4; → CeOP&sub3;O&sub9; +P&sub2;O&sub5;
The cerium pentaphosphate composition of the instant invention can
also be prepared by the method found in Par Muriel Bagieu-Beucher et Duc Tranqui:
Les Ultraphosphates de Terres Rares et D'yttrium du Type TP&sub5;O&sub1;&sub4;,
(The Ultraphosphates of Rare Earth and of Yttrium of the TP&sub5;O&sub1;&sub4;)
Bull. Soc. Fr. Mineral. Cristallogr. (1970), 83, 505-508, incorporated by reference,
for showing a preparation of a cerium pentaphosphate composition. The article discloses
a method of preparing ultraphosphates by a mixture of rare earth oxide and an
orthophosphoric acid in excess which is calcined for one or two days at temperatures
between 350°C and 750°C forming crystals. Further, the ultraphosphates can be synthesized
in a polycrystalline state by calcining for a day at a temperature of about 500°C,
a mixture in stochiometric proportions of rare earth oxide and biammonium phosphate.
A typical procedure to prepare the cerium pentaphosphate composition
of the instant invention is as follows: Cerium oxide and ammonium dyhydrogen phosphate
are mixed, ballmilled and then calcined to initiate a solid state reaction resulting
in cerium pentaphosphate powder. The cerium pentaphosphate powder is then prepared
into source wafers for the phosphorus doping of the semiconductor elements. Generally,
the source wafer is prepared by making a slurry of the cerium pentaphosphate powder
and water. Then the binding agents and/or additives are added to slurry. The mixture
is then heated resulting in the dopant source.
Generally, the dopant source of this invention can be used in any
appropriate solid form. The solid dopant can be formed in any convenient size
and shape, but typically it is formed in substantially the same or slightly larger
size and shape as a semiconductor body or wafer that it will be doping. The dopant
can be used in any appropriate form and/or on any universal substrate including
but not limited to powders of various coarseness; particulates; molded bodies;
pressed bodies; wafers; ceramic foams; for example, silicon carbide foam, silicon
nitride foam and the like; glass bodies; boats; crucibles; ceramic porous bodies;
coated onto a reaction vessel and the like. The particulate of the dopant source
can be formed by milling, grinding, jet milling, water milling, screening and the
like. The cerium pentaphosphate if employed on a universal substrate can be applied
by conventional methods such as dipping, coating, spraying and the like. The rate
of doping and lifetime of the product is dependent on the form of the source wafer
employed in the diffusion process.
The cerium pentaphosphate source may be used with binding agents
at about 0% by weight to about 20% by weight of the dopant, preferably 5% by weight
to about 10% by weight of the dopant. The weight percent of the binder is dependent
upon the annealing time, milling time, manufacture of the source wafer, cost, purity
and the like. Typical binders include but are not limited to inorganic binders
such as silicates, colloidal silica, colloidal alumina, colloidal aluminates,
colloidal silicates, colloidal silicon oxide, crystalline silica, silicic acid,
phosphosilica gels, metallic oxides and the like.
Other additive/dispersants may also be included such as surfactants
that vaporize off during processing such as sodium-free/non-ionic surfactants and
include, but are not limited to surfactants sold under the trade names Tergitol
(available from Union Carbide Co.), Nyacol, Nekal and the like. Other additives
include fluxing agents, which leave a residue in the doping source that may enhance
the phosphorus to vaporize and include, but are not limited to barium oxide, cesium
chloride and the like. The weight percent of the additives/dispersants is dependent
on the type and purpose of additives such as to control viscosity of the source
wafer or achieve sprayability of the source wafer and are from about 0% by weight
to about 10% by weight and generally less than 1% by weight.
The binding agent and/or additive/dispersant is employed to provide
strength and coating integrity and control of doping profiles in the silicon as
evidenced by sheet resistance. It is important that the amount and type of any
binder and/or additive/dispersant does not adversely affect the phosphorus doping
or contribute undesirable diffusible impurities which adversely affect the properties
of the dopant and/or the semiconductor body.
Generally, the method of doping of the semi-conductor body such as
silicon comprises diffusing phosphorus into a semi-conductor silicon body by positioning
at least one silicon body, in the vicinity of the dopant source, in the furnace
and then subjecting the silicon body and dopant source to a temperature in the
range of 800°C to 975°C and preferably 825°C and 950°C and under controlled atmosphere.
The dopant source and silicon body may be placed in vessels such as diffusion
boats, molded bodies and the like. The silicon body may have appropriate conventional
masking patterns typical to the semiconductor industry. At these temperatures,
the dopant source liberates phosphorus oxide vapors in particular P&sub2;O&sub5;
vapors which contact the surface of the silicon body that requires doping. This
process is conducted for a sufficient period of time to permit the diffusion of
the phosphorus into at least a portion of the surface of the silicon body to form
a diffused region therein. Generally, the doping occurs in the range of about 10
minutes to about 2 hours and preferably in the range of about 15 minutes to about
1 hour. The doping process is further controlled by the use of free-flowing inert
carrier gases such as argon, nitrogen or the like. The carrier gas does not enter
into a chemical reaction between the phosphorus vapors and the silicon surface.
The invention is further illustrated by the following examples, although
it is understood that the examples are intended merely for purpose of illustration
and are not intended to limit the scope of the invention.
SPECIFIC EMBODIMENTS OF THE INVENTIONSynthesis of Cerium Pentaphosphate Powder
Cerium pentaphosphate was prepared with rare earth oxide of cerium
oxide and ammonium dyhydrogen phosphate. The synthesis procedure was as follows:
1) about 2770g of ammonium dyhydrogen phosphate was mixed with about 753g cerium
oxide and 10 lb of standard milling medium, and ball milled for about 20hrs at
2) the firing process was either a continuous firing process or a low/high
a) the continuous firing process was as follows:
b) the low/high firing process was as follows:
i) Low Firing Processing:
ii) The soft material was scraped from the reaction box, ground to a finer
powder and then returned to the reaction box.
iii) High Firing Processing:
3) the composition was furnace cooled and the soft material, i.e. cerium pentaphosphate
powder was separated and removed from the furnace,
4) the synthesis process can take place on a universal substrate wafer (i.e.
silicon carbide foam wafer or its equivalent).
Synthesis of Cerium Pentaphosphate Source Wafers
Cerium pentaphosphate wafers were prepared for phosphorus doping
experiments with the cerium pentaphosphate powder. The procedures for the preparation
for spray coating cerium pentaphosphate source wafers were as follows:
1) About 500g of cerium pentaphosphate powder was mixed with about 61g of colloidal
silica in 800g of water, about 2.5g TMN-3 Surfactant (0.5g of WP-13 Surfactant
could be used in place of the TMN-3 Surfactant) and about 3.8g of TMN-6 Surfactant
(surfactants available from Union Carbide, Tergitol Nonionic Surfactants) were
added to the mix to make a slurry as follows:
a) The cerium pentaphosphate powder and water were milled for about 16 hours;
b) the colloidal silica was added and milled in the cerium pentaphosphate water
mixture for about 1 hour; and
c) the surfactants were then added to the slurry mixture and milled for about
2) the cerium pentaphosphate slurry mixture was spray coated on the silicon
carbide substrates; and
3) the spray coated silicon carbide wafer was then placed in a furnace at about
850°C for about 1 hour in air.
The procedure for dip coating the cerium pentaphosphate source wafers
were as follows:
1) About 300g of cerium pentaphosphate powder was mixed with about 548g of
water and about 15g of phosphorus silicate gel,
2) the powder, water and gel mixture were milled for about 14 hours,
3) the mixture was then stir mixed with about 200g of silicon pyrophosphate
(PH-1000n - trade name) slurry,
4) the mixture slurry was then used to dip coat the silicon carbide wafers
with a single drying, and
5) the dip coated silicon carbide wafers were sintered at about 850°C for about
1 hour in air in a covered fused silica container.
The source wafer and silicon carbide wafer were placed in a boat
and were pushed into a furnace. The wafers were preheated to about 700°C for about
10 minutes in a nitrogen atmosphere of about 5 1/min. After the wafers were preheated,
they remained in the furnace at about 700°C for about 10 minutes to stabilize.
The furnace was ramped up to about 850°C, which took about 20 minutes. The wafers
were then heated at about 850°C for about 60 minutes in the nitrogen atmosphere
for transfer of the phosphorus oxides to the silicon to occur. Then the furnace
was ramped down to about 700°C, which took about 20 minutes. The boat with the
wafers was then removed from the furnace, which took about 10 minutes.
The source wafers and silicon carbide wafers had a diameter of about
75 millimeters and the diffusion tube had a diameter of about 165 millimeters.
Controls were used of The Carborundum Company PH-950 (trade name)
dopant source, a silicon pyrophosphate PH-1000n (trade name) dopant source, both
high temperature phosphate dopant sources.
Thermogravimetric Analysis (TGA) was performed on the source wafers
to measure the weight change, which indicates where the dopant evolves from the
dopant source. TGA is a method of studying the chemical reactions occurring to
the source wafers within the furnace. In a TGA, the weight of a specimen is monitored
as it is taken from various temperature processes. The results are presented in
Figure I for cerium pentaphosphate powder at 800°C, 850°C and about 950°C in argon
and in Figure II for PH-1000n at 800°C, 825°C and 850°C in argon.
The cerium pentaphosphate shows small weight loss at 800°C, measurable
weight loss at 850°C and rapid weight loss at 950°C. As shown in Figure II, the
weight loss of PH-1000n was lower than the cerium pentaphosphate at the same temperatures.
A comparison shows that there is about a 100°C temperature difference achieving
comparable rate of decomposition of the source wafer.
The glass thickness test demonstrates the formation of phosphosilicate
glass on the silicon body which should be at least equal to or greater than 200Å,
and is a prerequisite for effective doping. Diffusion runs were performed with
cerium pentaphosphate, as shown in Table I and Figure III. This demonstrates doping
caracteristics at low temperatures.
The sheet resistance test shows that the electrically active species
of phosphorus has gone into the silicon. The lower the sheet resistance the more
electrically active phosphorus has penetrated the silicon. One and two-hour diffusion
runs were performed with cerium pentaphosphate solid wafers. Table II and Figure
IV show the sheet resistance for cerium pentaphosphate. This demonstrates doping
characteristics at low temperatures.
The lifetime of the cerium pentaphosphate source was studied over
200 hours of use time at 850°C doping runs. The glass thickness as shown in Figure
V decreased after the initial increase as use time increased. This demonstrates
that the glass thickness after 200 hours of use is still over 200Å, which is the
minimal thickness required to satisfactorily dope silicon. Figure VI shows that
the sheet resistance is nearly constant which demonstrates controlled doping of
silicon for a minimum of 220 hours of use time.
Although the invention has been described in detail through the proceeding
examples, these examples are for the purpose of illustration only and it is understood
that variations and modifications can be made by one skilled in the art without
departing from the spirit and scope of the invention.
A low temperature dopant source for the vapor phase transport of phosphorus
oxides to a silicon body comprising cerium pentaphosphate composition, said composition
capable of dissociating in the temperature range of about 800°C to about 975°C.
The dopant source of claim 1 wherein the dopant source is in a solid form and
is in a form selected from the group consisting of powders of varying coarsenesses;
particulates; molded bodies; pressed bodies; wafers; ceramic foams selected from
a group consisting of of silicon carbide foam, silicon nitride foam and combinations
thereof; glass bodies; boats; crucibles; ceramic porous bodies; coated onto a
reaction vessel and combinations thereof.
The dopant source of claim 1 wherein the particulate of the dopant source can
be formed by milling, grinding, jet-milling, water-milling, screening and combinations
The dopant source of claim 2 wherein the cerium pentaphosphate is employed
on a universal substrate and wherein it is applied onto such universal substrate
by a method selected from the group consisting of dipping coating, spraying and
The dopant source of claim 1 wherein the dopant is employed with binding agents
selected from the group consisting of silicates, colloidal silicates, colloidal
alumina, colloidal aluminates, colloidal silicon oxide, cyrstalline silica, silicic
acid, phosphosilicate gels, metallic oxides and combinations thereof; and with
additives and surfactants selected from the group consisting of surfactants, in
particular sodium-free/non-ionic surfactants and combinations thereof, fluxing
agents, in particular barium oxide, cesium chloride and combinations thereof.