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Borophosphosilicate Glass Films in Silicon Microelectronics, Part 1: Chemical

Vapor Deposition, Composition, and Properties

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Russian Microelectronics, Vol. 33, No. 5, 2004, pp. 271–284. Translated from Mikroelektronika, Vol. 33, No. 5, 2004, pp. 334–351.
Original Russian Text Copyright © 2004 by Vasilev.

MATERIALS AND PROCESSES FOR VLSI

Borophosphosilicate Glass Films in Silicon Microelectronics,

Part 1: Chemical Vapor Deposition,
Composition, and Properties
V. Y. Vasilev1
Institute of Semiconductor Physics, Siberian Division, Russian Academy of Sciences, Novosibirsk, Russia
e-mail: vladislav_v_2000@yahoo.com
Received April 29, 2003

Abstract—The first part is presented of a review that summarizes the results of 20-year experimental research
into CVD thin films of borophosphosilicate glass intended to serve as the premetal dielectric in multilevel met-
allization systems. The deposition methods, composition, and properties of the films are considered.

1 1. INTRODUCTION independent of the ways in which the material has been

With multilevel metallization systems, the transistor
layer is separated from the first metallization layer by a
dielectric film called the premetal dielectric, as illus-
trated in Fig. 1. The premetal dielectric prevents the
migration from the metal into the transistor layer as
well as providing a smooth surface for the conducting
tracks.
In the mid-1970s, premetal dielectrics were phos-
phosilicate-glass (PSG) films about 1 µm thick with a
phosphorus content of up to 13 wt % (about 30 wt %
P2O5). PSG is a getter toward alkali metals and can be
planarized by viscous flow. On the other hand, its flow
temperature is as high as above 1000°C. Furthermore,
the phosphorus reacts with the moisture to produce
orthophosphoric acid, which attacks the aluminum
[1−4].
In the early 1980s, borophosphosilicate glass
(BPSG) was proposed as an alternative premetal dielec-
tric [5]. BPSG contains up to about 30 wt % B2O3 and
P2O5 taken together (9.6–19.2 wt % B2O3 and 6.9–
13.8 wt % P2O5), or 3–6 wt % B and 3–7 wt % P. With
about two-thirds of P2O5 replaced by B2O3, the prob-
lem of corrosion was overcome and the flow temper-
ature was greatly reduced. The latter feature makes
BPSG suitable for use with short-channel and shal-
low-junction transistors and with radiation-hardened
devices. Although BPSG films were first employed
in circuits of minimum feature size over 1 µm, they
are also compatible with technologies well below
that level.
This paper is the first part of a review of BPSG as a
premetal dielectric, summarizing the results of 20-year
experimental research. The emphasis is on the follow-
ing topics. First, the properties are examined that are
1 Previously transliterated as Vassiliev and Vasil’ev.
deposited and processed. Second, the relationship is
investigated between the behavior of the material and
the deposition technique. Third, the similarities are
identified between BPSG and other glass systems with
actual or potential microelectronic applications, such as
PSG and borosilicate glass (BSG). Some of the data to
be reviewed were presented in [6, 7].
Part 1 is concerned with the chemical vapor deposi-
tion (CVD), composition, and properties of BPSGs,
including the major methods and mechanisms of film
growth. Part 2 will deal with BPSG structure and appli-
cations.
12
11
10
8
9
7 6
5
4
3
2
1
Fig. 1. Multilevel metallization on a silicon chip (schematic
diagram): (1) substrate, (2) isolation trench, (3) source or
drain region, (4) gate oxide, (5) poly-Si gate, (6) premetal
dielectric, (7) contact to silicon, (8) interlevel insulator,
(9) conducting track, (10) passivation dielectric, (11) con-
tact pad, and (12) opened contact window.

1063-7397/04/3305-0271 © 2004 MAIK “Nauka /Interperiodica”

272
2. CVD METHODS AND MECHANISMS
FOR BPSG FILMS
2.1 Strategies
BPSG thin films are deposited on circular wafers in
different types of flow reactor by atmospheric-pressure
CVD (APCVD), reduced-pressure CVD (RPCVD), or
low-pressure CVD (LPCVD). Increased reaction rates
at low pressures can be obtained by plasma-enhanced
CVD (PECVD). The evolution of reactor designs was
driven by growth in wafer diameter and by tightening
up on the uniformity of film thickness and properties.
Initially, wafers were treated in a batch manner with up
to hundreds of wafers per batch; the films were depos-
ited with low rates and modest thickness uniformity.
This approach gave way to single-wafer processing in
the early 1990s. Modern technologies allow complete
automation of the process as well as providing high
deposition rates and uniformity.
Figure 2a is the sketch of an LPCVD reactor for
batch processing. Figure 2b outlines a reactor for
RPCVD or PECVD in a single-wafer mode.
2.2 Major Reactions and Technologies
A thin film of BPSG is deposited on a heated
wafer by a number of irreversible chemical reac-
tions between continuously fed reagents and/or
intermediate reaction products. The deposition is a
multistaged process including gas-phase reactions,
the transport of source species and intermediate
products to the wafer surface, surface processes, het-
erogeneous reactions, etc.
The input reagents have been various combinations
of the hydrides SiH4, PH3, and B2H6; esters of silicic,
boric, orthophosphorous, or orthophosphoric acid;
chlorides of boron or phosphorus; etc. The deposition
involves oxidation of these substances. It must use as
strong an oxidizing agent as pure oxygen or its mixture
with ozone (N2O is inadequate).
3 (a)
Fig. 2. Sketches of CVD reactors for (a) batch and (b) single-wafer processing: (1) reagent-gas feed, (2) exhaust, (3) cylindrical
heater, (4) wafer(s), and (5) gas distributor (also serving as an RF electrode in plasma reactors).
VASILEV
The oxidation is still poorly understood. It is
thought to occur by independent mechanisms such as
SiH4 + O2 SiO2 + 2H2, (1)
4PH3 + 5O2 2P2O5 + 6H2, (2)
2B2H6 + 3O2 2B2O3 + 6H2. (3)
However, the oxidation may well have more by-
products, e.g., water, depending on the process con-
ditions.
Industrially, BPSG films are mostly deposited by
two alternative processes. One of them uses SiH4 in
combination with hydrides, chlorides, or esters at 350–
450°C and atmospheric or a low pressure. The other
employs (C2H5O)4Si, known as tetraethylorthosilicate
(TEOS), in combination with phosphine or esters of
boric, orthophosphorous, or orthophosphoric acid. The
TEOS process is implemented in three versions:
(i) LPCVD at 650–725°C, (ii) PECVD at about 400°C,
and (iii) APCVD or RPCVD at 400–500°C using an
oxygen–ozone mixture with 4–12 wt % of ozone.
A third alternative has recently emerged, which
combines CVD with argon sputter deposition in a high-
density plasma (HDP). Although this approach was
designed to make SiO2 or PSG films from hydrides, it
is in principle suitable for BPSG deposition.
Table 1 presents a comparison of industrial CVD
techniques for BPSG and other glasses. Details of the
process equipment and CVD methods are given in
[1−4, 6–14]. All these techniques can yield BPSG films
in which boron and phosphorus account for about 6–
8 wt % each. They are also suitable for the deposition
of SiO2, PSG, and BSG films.
2.3 Deposition Kinetics
CVD processes are commonly characterized in
terms of process temperature, reagent pressures and
concentrations, gas flow rate, etc. Research into BPSG
deposition kinetics is reviewed in [6, 7, 15–25]. The
5 (b) 1
4
3 2 4
RUSSIAN MICROELECTRONICS Vol. 33 No. 5 2004
 Basic features of industrial CVD processes for glass films

Deposition method
Process characteristic or parameter
APCVD, LPCVD LPCVD APCVD, LPCVD PECVD HDPCVD

Method # 1 2 3 4 5

Deposition mode Batch mode Single-wafer mode

Wafer diameter, mm 60, 76, 100 100, 150 150, 200 200 200

RUSSIAN MICROELECTRONICS
Temperature, °C 400–450 700–850 440–500 380–420 380–625

Plasma enhancement No No No Yes Yes

Vol. 33
Source of silicon SiH4 (C2H5O)4Si (C2H5O)4Si (C2H5O)4Si SiH4

Sources of boron and phosphorus PH3, B2H6, BCl3, esters PH3, PCl3, esters Esters Esters PH3

No. 5
Oxidizing agent O2 O2 O3–O2 mixture O2 O2

Pressure, torr 0.5–2 0.5–2 150–760 5–13 ≈5 × 10–3

2004
Carrier gas N2–Ar mixture Ar He N2 Ar

Deposition rate, Å/min 300–5000 (APCVD), Up to 200 3000–5000 Up to 10000 ≈4000

50–150 (LPCVD)

Film thickness uniformity, ±% 10 3 1.5 2 2

Effect of phosphorus on reaction rate Acceleration Acceleration Acceleration Acceleration Not available

Effect of boron on reaction rate Inhibition Acceleration Acceleration Acceleration Not available

τmax, s ≤0.025 ≈0.05 ≈0.05 Not available Not available

keff, cm/s 2.0–2.6 0.8–1.1 1.1–1.5 2–5 Not available

BOROPHOSPHOSILICATE GLASS FILMS IN SILICON MICROELECTRONICS

RMS height of surface ≈120 (APCVD), Not available ≈21 (APCVD), ≈8 ≈5

irregularities, Å ≈25 (LPCVD) ≈9 (LPCVD)

Conformality (step coverage), % 30–40 60–80 60–80 10–30 Not available

H/G2 ratio, µm–1 Not available Not available <4 <1 >20
273
274
following basic features have been revealed in the case
of silicon wafers with flat surfaces. The deposition
reactions are of first order in the silicon compound; they
occur at considerable excess of the oxidizing agent and
so may be taken to be of pseudozero order in the oxidiz-
ing agent. The activation energy of oxidation has been
variously reported to be 62–209 kJ/mol except for
PECVD, in which it is lower by an order of magnitude.
The phosphorus and boron compounds employed
have an important part in the deposition. Figure 3a
illustrates this by showing the ratio of the glass deposi-
tion rate W to the SiO2 deposition rate W0 as a function
of boron-to-silicon or phosphorus-to-silicon molar
ratio in the gas phase. Phosphorus compounds are
known to accelerate the oxidation of silicon com-
pounds, reducing the activation energy by a factor of
1.3 to 3. The acceleration is accompanied by a propor-
tional increase in phosphorus concentration for both
PSG and BPSG; it also degrades film uniformity and
enhances the formation of aerosol by-products. Maxi-
mal acceleration (by a factor of 3 to 7) is obtained with
TEOS–phosphine combinations; it is minimal with
silane. It is known that the oxygen oxidation of silane,
phosphine, and other phosphorus compounds occurs by
the free-radical chain mechanism [26, 27]. Further-
more, it has been established that the acceleration of
oxidation lessens as one passes from PH3 to PCl3 to
esters. These findings suggest that the acceleration
should be taken to indicate the free-radical chain mech-
anism of the oxidation. However, it has also been found
that boron compounds tend to inhibit CVD involving
silane and phosphine. This fact should imply the oxida-
tion by the free-radical chain mechanism being inhib-
ited. The conclusion is supported by reduced deposition
rate when silane oxidation is used, as well as by a lower
W/W0 (a)
8 Aerosol
6 PSG, TEOS
BSG, TEOS
4
PSG, SiH4
2
BSG, SiH4
0 1 2 3
B/Si or P/Si molar ratio
Fig. 3. Acceleration and inhibition of oxidation by boron and phosphorus compounds: (a) the ratio of the glass deposition rate W to
the SiO2 deposition rate W0 as a function of B/Si or P/Si molar ratio in the gas phase and (b) deposition rate vs. residence time for
a reference (full curve), an accelerated (dashed curve), and an inhibited (dot-and-dash curve) oxidation reaction.
VASILEV
phosphorus content in glasses obtained by adding
boron compounds to the source gas. By contrast, boron
compounds accelerate the relatively slow oxidation of
TEOS.
The above reasoning is underpinned by atomic-
force microscopy measurements of surface roughness
for BPSG films produced by different methods [28]. In
particular, the phosphorus acceleration results in higher
surface roughness, and the boron inhibition leads to
lower roughness. Averaged values of surface roughness
are given in table.
In short, phosphorus compounds enhance the incor-
poration of boron into the film, whereas boron com-
pounds inhibit the incorporation of phosphorus.
Figure 3b illustrates CVD acceleration and inhibi-
tion in a model flow reactor. It shows deposition rate as
a function of residence time for a reference, an acceler-
ated, and an inhibited oxidation reaction. The time
curves are derived from experimental data, with the res-
idence time τ calculated as τ = x/υ, where x is the wafer
coordinate in the reactor in centimeters and υ is the gas
flow speed in centimeters per second. Such curves were
found to be the same for all types of flow reactor exam-
ined, so that the residence time should be equivalent to
the reaction time [29]. Accordingly, the shape of an
experimental time curve can be used to identify the
CVD mechanism. It has thus been found that phospho-
rus compounds exert a major influence on deposition
kinetics: (i) They accelerate the reaction and shift the
time curve toward shorter residence times. (ii) They
enhance the formation of aerosol by-products. When
the oxidation reactions are inhibited by boron com-
pounds, the time curve is shifted toward longer resi-
dence times, and aerosol by-products are not observed.
(b)
W
τmax
τ
RUSSIAN MICROELECTRONICS Vol. 33 No. 5 2004
 BOROPHOSPHOSILICATE GLASS FILMS IN SILICON MICROELECTRONICS
It follows from the above that process optimization
must consider residence time as well as directly mea-
surable parameters (temperature, pressure, and concen-
trations). In particular, the CVD rate is maximal and the
high-purity reagents are used most efficiently if the res-
idence time at the wafer surface corresponds to the
maximum deposition rate on the time curve.
The stated conditions also minimize the formation
of aerosol by-products. It has been found for different
CVD processes that there exists a deposition rate above
which the film shows particulates (the limiting rate is
about 1.5 to 2 times higher than the deposition rates
given in Table 1). In Fig. 3b the large arrows indicate
the changes in deposition conditions that enhance the
unwanted aerosol effects.
2.4 Deposition Mechanisms
The effective CVD rate keff has been proposed as a
characteristic that would enable one to quantitatively
compare oxidation processes. It is proportional to the
ratio of the maximum CVD rate as given by the time
curve (Fig. 3b) to the concentration of the silicon com-
pound in the gas phase (implying that the CVD process
has been optimized). A motivated definition of keff is
presented in [13, 18, 23, 25].
For SiO2 and glasses other than BPSG, keff was
found to range from 0.3 to 10 cm/s. For the BPSG pro-
cesses examined, it varies over a narrower range, 1.1–
2.5 cm/s. It is seen that the silane and the TEOS process
have similar characteristics for glasses of similar com-
position.
The influence of phosphorus and boron compounds
on the oxidation rate is evidence that, unlike Eqs. (1)–
(3), the oxidation reactions are interlinked with each
other via intermediate products. The kinetic data relat-
ing to phosphorus compounds strongly indicate that all
CVD processes of BPSG (as well as PSG) are governed
by closely related mechanisms that involve free radicals
produced by interaction between the phosphorus com-
pound and the oxidizing agent.
Repinskii [30] proposed that CVD be treated as con-
sisting of multiple pathways and steps. Accordingly, a
simplified, three-pathway scheme was constructed as
shown in Fig. 4a. Pathway I is slow processes governed
by a heterogeneous mechanism. Pathway II is fast reac-
tions including plasma-enhanced ones; it consists of
two steps: homogeneous intermediate-product forma-
tion and heterogeneous product consumption (either
one can be the rate-determining step). Pathway III is
meant to account for the structural inhomogeneity of
films (surface irregularities, particulates, and powdery
deposit).
Figure 4b illustrates how the above scheme works in
the TEOS deposition of SiO2 and glass films [21–23,
25]. This process is notable for the largest number of
reactants and the highest acceleration. Pathway I repre-
sents the formation of SiO2 and is implemented as
RUSSIAN MICROELECTRONICS Vol. 33 No. 5 2004
275
either the high-temperature pyrolysis of TEOS at the
surface or the low-temperature reaction between
adsorbed TEOS and adsorbed ozone. The latter method
yields SiO2 films of less homogeneous structure (with
higher roughness and porosity) compared with ones
produced with oxygen serving as the oxidizing agent. If
boron and phosphorus compounds are added to the
source gas, CVD follows pathway II and involves phos-
phorus radicals (labeled R*), the homogeneous forma-
tion of the intermediate products IPX and IPY , and their
heterogeneous conversion to the glass. The homoge-
neous formation of IPX is believed to be the rate-deter-
mining step of CVD for PSG and BPSG, whereas the
heterogeneous conversion of IPY is believed to play the
same role for BSG. With pathway III, the aerosol is
thought to be produced as clusters, some of which
should contain boron and phosphorus oxides.
2.5 Step Coverage and Gap Filling
For patterned wafer surfaces the deposition rate of
BPSG varies from point to point for all the CVD pro-
cesses examined. The nonuniformity is characterized in
terms of the percentage ratio of the vertical to the lateral
glass thickness in relation to a surface feature, as shown
in Fig. 5. This characteristic is known as the conformal-
ity or the step coverage [1]. A correlation was observed
between measured conformalities and keff [34]. For
CVD processes using organic compounds, the confor-
malities and the corresponding values of keff were found
to be higher and lower, respectively.
With ultrasmall gaps between surface features, the
problem arises of void-free gap filling [14, 31–35]. It
has been proposed that the gap-fill capability of a CVD
process be evaluated by the H/G2 ratio as illustrated in
Fig. 5. This parameter measures the complexity of sur-
face patterns that can be covered by the CVD process.
Some experimental values of the conformality and the
H/G2 ratio for rectangular gaps are presented in table.
3. BPSG FILM COMPOSITION
Figure 6 gives the boron and phosphorus concentra-
tions of BPSGs examined. The levels and lateral pro-
files of these components are determined destructively
by spectrum analysis, etching, etc., or nondestructively
by infrared (IR) spectroscopy or x-ray fluorescence (the
latter approach requires calibration by destructive
methods).
To facilitate thermal-flow planarization, the compo-
sition should be just below the line representing the
crystallization of BPO4 in the SiO2–B2O3–P2O5 system
at over 950°C [36, 37].
With large excess of oxidizing agent, the glass has
an almost stoichiometric composition: it contains SiO2,
B2O3, and P2O5. The zero stoichiometric excess of sili-
con is inferred from the refractive index of the film
being in the range 1.44–1.48, as measured by ellipsom-
276 VASILEV

(a)
II III
Intermediate-product
formation Aerosol

I
Intermediate-
Diffusion product
Input reagents

diffusion

Heterogeneous Heterogeneous
step step

Deposited film Deposited film

(b)

Pathway I Pathway II Pathway III

O3 + TEOS + O2
PO(OC2H5)3

R* B(OC2H5)3

IPY
IPX

O3(ad) TEOS(ad)

Porous SiO2 Relatively porous Relatively porous

film glass film glass film
with clusters

Fig. 4. (a) Three-pathway scheme of CVD and (b) its application to the TEOS deposition of SiO2 and glass films.

etry. Phosphorus compounds are usually oxidized to
P2O5; however, ion-exchange chromatography mea-
surements sometimes detect phosphorus with an oxida-
tion number of +3 (concentration below about 1 wt %),
indicating P2O3 [38, 39]. This is typical of BPSG and
PSG obtained by LPCVD from hydrides at low temper-
atures [40]. Another example is PECVD using phos-
phine when the process is effected at an elevated radiof-
requency (RF) power and with inadequate excess of the
oxidizing agent or with a weak oxidizing agent. In
PECVD films, Si–P (130 eV) as well as P–O (134 eV)
bonds were detected by electron spectroscopy for
chemical analysis (ESCA) [41]. If the process involves
an ester and the oxidizing agent is used in large excess,
phosphorus is always observed with an oxidation num-
ber of +5. Likewise, PSG films made by a hydride HDP
process consistently show an oxidation number of +5
for phosphorus [35, 42]. Also note that postdeposition
thermal processing, even in an unreactive environment,

RUSSIAN MICROELECTRONICS Vol. 33 No. 5 2004

 BOROPHOSPHOSILICATE GLASS FILMS IN SILICON MICROELECTRONICS
d1
H
G
Fig. 5. Step coverage and gap filling.
increases the proportion of the phosphorus that has this
oxidation number [40].
If deposited in a proper way, BPSG films have uni-
form depth profiles of boron and phosphorus, as sup-
ported by secondary-ion-mass-spectroscopy (SIMS)
evidence [5, 40, 43, 44]. With method 3 (see table),
there are strong variations of boron and phosphorus
concentrations about the mean values; the magnitude of
variation may be 3–5 times larger as compared with
films made by method 4 [44].
Glassy films produced from TEOS or other esters
tend to contain carbon. For example, method-3 films
with a phosphorus concentration as high as 7 wt % and
with 3 wt % B display a uniform depth profile of carbon
at a level close to 1.05 × 1019 atoms/cm3 against 3.19 ×
1019 atoms/cm3 for films with 4 wt % P and 4.5 wt % B
[23].
Hydrogen is found in films obtained by any of the
methods considered. Generally, its concentration
increases if the CVD temperature is reduced to below
400°C. With method 3, as-deposited PSG and BPSG
films with 4 wt % B and 4 wt % P show uniform distri-
bution of hydrogen, whose initial concentration is
about 3 × 1020 atoms/cm3. With methods 4 and 5,
hydrogen concentrations were reported to be about 6 ×
1020 and 4 × 1020 atoms/cm3, respectively [45].
IR absorption spectra of BPSG films (Fig. 7a) have
the following main bands: 1050–1100 (Si–O), 1300–
1350 (P=O), and 1400–1450 (B–O) cm–1 [5, 6]. The
second and the third band are used to evaluate the boron
and phosphorus concentrations. The simultaneous oxi-
dation of silicon, boron, and phosphorus compounds
produces the groups (≡Si–O–)3P=O and (≡Si–O–)3B, so
that the bonds Si–O–B, Si–O–P, and P–O–B are
formed. The bond Si–O–B is easy to detect, appearing
at 900–950 cm–1; however, the IR absorption bands of
the bonds Si–O–P (
1145 cm–1) and P–O–B
RUSSIAN MICROELECTRONICS Vol. 33 No. 5 2004
277
d2
3
2
1
(
1100 cm–1) cannot be detected, because they are
within the strong band of Si–O [46].
On thermal processing at above 750°C, the refrac-
tive index of BPSG films becomes sensitive to phos-
phorus concentration, a property that was at one time
used by some researchers for analytical purposes. The
resulting densification enhances the P=O band slightly
and blue-shifts the Si–O band. The carbon concentra-
tion decreases by about an order of magnitude, espe-
cially in the case of oxidizing environment, and the
hydrogen concentration falls by about 30% [23, 45].
Long, high-temperature thermal processing reduces
the boron and phosphorus concentrations at depths
up to 0.05–0.1 µm, indicating their evaporation from
the film [44].
4. PHYSICAL AND CHEMICAL
PROPERTIES OF BPSG FILMS
BPSG films were examined by the methods used for
the characterization of insulator thin films in microelec-
tronics.
4.1 Surface Roughness and Defect Density
The inspection of BPSG thin films by the naked eye
or optical microscopy is usually performed immedi-
ately after the deposition. As-deposited films vary
greatly in texture. Qualitatively, they are commonly
characterized as specular, contaminated, matt, or hazy.
In the mid-1990s the atomic-force microscope emerged
as a tool with which to measure the surface roughness
of thin films. Below we present the conclusions of a
comparative investigation into the surface roughness
and defect density of BPSG films differing in composi-
tion [28].
The root-mean-square (rms) height of surface irreg-
ularities of films obtained by methods 3 and 4 from
TEOS is in the range 8–21 Å; rms heights 2.5–6 times
larger were observed in films deposited by method 1
278
[P], wt %
15
10
0 5
Fig. 6. The B and P concentrations of BPSG thin films produced by different CVD methods.
from silane at atmospheric or low pressure (see table).
This difference is evidence for intense gas-phase reac-
tions during the deposition of the latter films. In this
case the surface roughness of LPCVD films is a few
times lower than that of APCVD ones, presumably due
to a considerable difference in deposition rate. Also, the
surface roughness of BSG films is about half as large as
that of PSG and BPSG films fabricated under similar
conditions. This fact strongly indicates the inhibiting
influence of boron compounds on the gas-phase reac-
tions. With respect to SiO2 films, using the ozone–oxy-
gen oxidation of TEOS results in the rms irregularity
height approaching 60 Å. Values more than ten times
lower are obtained by introduction of boron- and phos-
phorus-containing esters, indicating a change in the
CVD mechanism.
In the BPSG case, heating starts to have an effect on
surface roughness once a point of about 750°C has been
reached, both the temperature and the duration of ther-
mal processing being critical. Note that the level 750°C
is equal to the flow temperature of the glasses consid-
ered.
Concerning defects in BPSG films, it is important to
distinguish between process-induced and postdeposi-
tion defects. The former are specific to the CVD
method and the process conditions including the state
of equipment. The density of process-induced defects is
measured immediately after deposition (it is currently
required that for defects larger than 0.2 µm the density
be less than 0.1 cm–2 on wafers with a minimum feature
size over 0.15 µm). Postdeposition defects are caused
by air moisture. Their density may grow by a few orders
of magnitude over a relatively short period, depending
VASILEV
BPO4 region
10 15
[B], wt %
on the glass composition. Further details will be given
later.
4.2 Gettering Capability
The gettering capability of BPSG films is due to a
fairly high concentration of phosphorus oxide, a well-
known getter for alkali-metal ions. It was convincingly
demonstrated in experiments using the 22Na isotope
[5, 47]. The element was introduced by applying
22NaCl to the film surface or by ion implantation, fol-
lowed by thermal processing at 430–500°C. The distri-
bution of sodium indicated that its ions were retained
by a gettering mechanism rather than a barrier one. A
similar mechanism was identified in PSG films, but
these showed a smaller amount of gettering, as evi-
denced by a larger proportion of sodium ions escaping
retention.
4.3 Wet and Dry Etching
If a BPSG film is etched with hydrofluoric acid, the
etch rate is known to vary with glass density and boron
and phosphorus concentrations. Pliskin’s etchant
known as the P-etch enables one to selectively check
the phosphorus concentration in SiO2 films [48, 49]. If
the hydrofluoric acid is mixed with a buffer, etch rate
varies inversely as boron concentration; this effect was
employed for rapid determination of boron [15, 19].
The etch rate usually lies between 5 and 300 Å/min,
depending on the HF concentration.
With the dry etching of BPSG films using fluorine-
containing reagents, the etch rate was found to be inde-
RUSSIAN MICROELECTRONICS Vol. 33 No. 5 2004
 BOROPHOSPHOSILICATE GLASS FILMS IN SILICON MICROELECTRONICS 279

Amount of IR absorption
(a)
0.8

0.7

0.6

0.5

0.4

0.3
4000 3500 3000 2500 2000 1500 1000 500
Wave number, cm–1
Amount of IR absorption
(b)

Method 4

Method 3

3800 3200 2600 2000 1400

Wave number, cm–1

Fig. 7. IR absorption spectroscopy of BPSG films: (a) the typical spectrum of an as-deposited film and (b) the spectra of films pro-
duced by methods 3 and 4 and subjected to autoclave stressing. The spectra of panel (b) are for 3200–3500 cm–1.

pendent of the glass composition for both as-deposited
and thermally treated films, possibly due to low con-
centrations of boron and phosphorus.
4.4 Stress in BPSG Films
It was expected that adding boron to PSG would
make it possible to lower the phosphorus concentration
in order to improve the passivation capability of the
glass films [50]. Aside from gettering, the phosphorus
concentration relates to the level of stress experienced
by the film; if the former is too high, microfissures arise
in thick films. However, BPSG is not used for passiva-
tion despite the fact that BPSG films fabricated by
method 1 have shown a compressive stress (minus sign)
a few times lower as compared with PSG ones pro-
duced under the same conditions.
Interlevel insulators made by plasma-enhanced
methods (including HDP ones) should have a compres-
sive stress of about (1.5–2) × 109 dyn/cm2. A desired
magnitude of stress is obtained by adjusting the RF
power, because it is this process variable that is inti-
mately related to the stress.
For as-deposited premetal dielectrics the sign and
magnitude of stress are of secondary importance,
because they will be subjected to thermal-flow pla-
narization. As-deposited BPSG films made by method
3 (an approach widely adopted by modern microelec-
tronics) have a tensile stress of (4.3–6.5) × 108 dyn/cm2,

RUSSIAN MICROELECTRONICS Vol. 33 No. 5 2004

280 VASILEV
whereas those obtained by method 4 show a compres-
sive stress of (4.0–6.0) × 108 dyn/cm2.
4.5 Effects of Thermal Processing
Thermal processing can greatly enhance relatively
small distinctions between as-deposited BPSG films.
One property that is affected by heating is the effective
density (or its reciprocal, called the porosity), as can be
inferred from shrinkage and etch-rate measurements.
At the present time the thermal processing of BPSG
films is most commonly the rapid thermal annealing at
700–900°C for 20–90 s. The resulting shrinkage of
films made by method 3 is 3.0–3.4% [51, 52]. With
30-min, 750°C furnace annealing, the same films
shrink by about 4.2%. It follows that longer treatment,
even at a lower temperature, should result in a denser
glass. The minimum amount of shrinkage, ~0.1%, was
observed in films produced by method 5 with sputter-
ing [35].
The amount of shrinkage depends on the boron-to-
phosphorus concentration ratio [B]/[P]: films with
[B]/[P] < 0.5 experience a shrinkage about half as large
as those with [B]/[P] ≥ 1; this fact points to a larger
effective density of the former films. Furnace anneal-
ing provides better densification of BPSG films and
so makes them more stable and more resistant to
moisture.
Also note that BPSG films obtained by method 3,
even thermally processed ones, were found to be far
more susceptible to hydrofluoric acid etching as com-
pared with films made by the other methods, an indica-
tion of higher porosity.
4.6 Moisture Effects
Under prolonged exposure to air, BPSG films react
with the ambient moisture. A widely used indicator of
moisture effects is the emergence of broad bands at
3650 and 3350 cm–1 in IR spectra, as shown in Fig. 7b.
These bands are commonly associated with hydroxyl
groups and absorbed water, respectively [21, 23, 44].
The latter band is red-shifted as the water concentration
in the film increases. Another indicator is the weaken-
ing of the band at 1300–1350 cm–1 (thermal processing
restores the intensity of the band if the amount of phos-
phorus evaporated from the film is not too large).
BPSG films made by method 3 were found to be the
most susceptible to moisture. SIMS measurements
have revealed that the hydrogen concentration in such
films grows by about an order of magnitude over three-
week exposure to air, reaching (1.6–3.0) ×
1021 atoms/cm3.
The effects of moisture depend on [B]/[P] as well as
([B] + [P]) in the film. They are strongest when
[B]/[P] > 1, whereas glasses with [B]/[P]
0.4 were
found to be the least susceptible to moisture [53].
RUSSIAN MICROELECTRONICS
The above is usually explained as due to these sim-
ple reactions [1, 48, 54, 55]:
H2O(g) H2O(ab), (4)
≡Si–O–Si≡ + H2O(ab) 2(≡Si–OH), (5)
(≡Si–O–)3P=O + H2O(ab) (≡Si–O–)3P(OH)2, (6)
where H2O(ab) and H2O(g) denote the absorbed water and
the moisture, respectively (notice that the equations
indicate the reasons for water being present in the film).
The reactions are reversible under thermal processing.
Concerning Eq. (6), some comments are in order. It
is known that a phosphorus in oxide systems is always
bound to four oxygens, an oxidation number of +5
being due to the P=O double bond. For this reason, the
formation of the (≡Si–O–)3P(OH)2 group appears to be
unrealistic. Instead, we propose the equation
( ≡Si–O– ) 3 OP + H 2 O (ab) ≡Si–OH +
(7)
+ ( ≡Si–O– ) 2 OPOH.
Equation (7) also explains the leaching of phospho-
rus from films and the concomitant formation of ortho-
phosphoric acid: this is seen as the product of the grad-
ual substitution of –OH for ≡Si–O– in the (≡Si–O)3P=O
group by reaction with absorbed water.
For BSG films, we are unaware of any published
mechanism of moisture effects.
From the standpoint of the Lewis theory, one could
relate the higher moisture susceptibility of boron-rich
BPSG films to the fact that B2O3 is a strong Lewis acid
and coordinates even to weak bases to produce tetrahe-
dral compounds [56]. Accordingly, the three-coordi-
nate boron atom in (≡Si–O)3B might be seen as an elec-
tron-pair acceptor, whereas the oxygen of a water mol-
ecule (a Lewis base) as an electron-pair donor.
However, it should be pointed out that the donor capac-
ity of the oxygen is insufficient to make a coordinate
bond to a boron, so that a tetrahedral compound cannot
be formed (the addition reaction between H2O and
B2O3 produces only meta- and orthoboric acid). Conse-
quently, the (≡Si−O)3BOH2 group in which the boron is
equally coordinated to the four oxygens is unlikely to
be stable. Also note that the water molecules tend to
migrate from boron to boron, penetrating into the film
[54]. The interaction suggests the formation of the
[(≡Si–O)3B] ⋅ H2O group, as with the addition of water
to crystal hydrates. Also plausible is the reaction
( ≡Si–O– ) 3 B + H 2 O (ab) ≡Si–OH +
(8)
+ ( ≡Si–O– ) 2 BOH.
In particular, this explains the leaching of boron
from films as due to the gradual substitution of –OH for
≡Si–O in the (≡Si–O)3B group.
The presence of hydrogen in as-deposited glass
films was initially attributed to the moisture only [55].
Two more sources of hydrogen were identified by
Vol. 33 No. 5 2004
 BOROPHOSPHOSILICATE GLASS FILMS IN SILICON MICROELECTRONICS 281

[B] + [P], wt % Penetration depth, µm

12 1.00

0.75
8

0.50

Moisture-resistant
4 composition area boundary
Water penetration 0.25
depth

0
0 20 40 60 80 100
[B]/([B] + [P]), %

Fig. 8. Moisture susceptibility of autoclave-stressed BPSG films. The dashed curve shows water penetration depth against relative
boron content, calculated from the data in [54]. The full curve outlines the area of compositions with which the BPSG films remain
defect-free for 24 h when exposed to moisture [53].

SIMS profiling for hydrogen and carbon in the case of
BPSG films made by APCVD or LPCVD using esters,
which also provided more accurate estimates of water
concentration [23, 45, 51]. One of the sources is the
water produced by oxidation of the esters; it accounts
for about 80% of the initial hydrogen concentration.
The other is the –OC2H5 groups, accounting for about
20%; they result from the incomplete oxidation of the
silicon, boron, and phosphorus alkoxy compounds in
the process gas.
The initial water concentration was estimated at
below 0.15 wt %, the mass spectrometer being cali-
brated against the thermal-desorption data from [55].
After three-week exposure to air, the water concentra-
tion in the films was estimated at about 1.8 wt % (from
hydrogen profiles).
BPSG films obtained by plasma deposition (espe-
cially HDP one) were found to have a water concentra-
tion of the order of 0.1% at most, even after long-term
exposure to air.
4.7 Autoclave Stressing
The difference between BPSG films in moisture sus-
ceptibility can be made noticeable by accelerated
stressing in an autoclave. An example is 168-h treat-
ment at 121°C, 1.2 atm, and a 100% relative humidity.
SIMS profiling makes it possible to measure the leach-
ing of phosphorus and boron from the films, enabling
one to assess the stability of the glass. In the case of
phosphorus-rich (over 9 wt % P) BPSG films obtained
by method 1, the strong leaching of phosphorus in
autoclave stressing was once attributed to the presence
of phosphorus oxide clusters in the BPSG [54]. With
respect to the leaching of boron, we are unaware of
published reports on this effect in the context of BPSG
films, although boron-rich monolithic BSG is known
to experience the leaching of boron when boiled in
water [48].
It has been inferred from thermal-desorption mea-
surements that the moisture susceptibility of autoclave-
stressed BPSG films depends on [B]/[P]: if [B]/[P] > 1,
the films tend to show bulk absorption of water; other-
wise, water is confined to a near-surface layer [54]. Our
treatment of the same data yielded a more accurate
value of the threshold: [B]/[P] = 0.4 [53]. This is illus-
trated by the dashed curve of Fig. 8.
The experimental results imply that BPSG films
made by method 3 are the most susceptible to moisture.
Having been stressed under the above conditions, they
show the highest intensity in the band 3200–3600 cm–1
(Fig. 7b). SIMS profiles indicate the pronounced leach-
ing of both boron and phosphorus at depths up to about
0.2 µm. Also note that water absorption and the leach-
ing become progressively stronger as ([B] + [P]) is
increased from about 6 wt %. At the same time,
PECVD films of approximately the same composition
displayed the leaching of boron and phosphorus only
within 0.05 µm from the surface [44].

RUSSIAN MICROELECTRONICS Vol. 33 No. 5 2004

282 VASILEV
4.8 Relationship between Deposition Methods
and Film Properties
It is apparent that the variability of properties
observed in BPSG films is related to differences in dep-
osition method, composition, and structure. The effec-
tive density or the porosity is probably the most impor-
tant film property. Regrettably, there appear to be no
published reports on the direct measurements of effec-
tive density for BPSG films. It follows from the litera-
ture that the highest porosity is observed in films made
by method 3 that includes the low-temperature oxida-
tion of an ester with an O3–O2 mixture; this applies to
SiO2, PSG, BSG, and BPSG. The lowest porosity is
associated with plasma methods, especially with HDP
deposition. For SiO2 and BSG, the highest porosity is
explained as due to a small keff. Recall that fast CVD
reactions can be seen as a two-step process (pathway
II), the steps being homogeneous intermediate-product
formation and heterogeneous product consumption.
Since the latter is the rate-determining step for the
glasses considered, heterogeneous glass structures are
produced (Fig. 4b). The porosity can be greatly reduced
by making the intermediate-product formation the rate-
determining step.
5. ELECTRICAL PROPERTIES OF BPSG FILMS
Premetal dielectrics should be good getters and
should readily lend themselves to thermal-flow pla-
narization. On the other hand, they do not need to show
unusual electrical performance. Accordingly, the elec-
trical properties of BPSG films were examined by con-
ventional methods using the metal–insulator–silicon
structure. The BPSG films contained 2 to 7 wt % of
boron and phosphorus. Regrettably, there appear to be
no literature data on the relationship between the elec-
trical properties of the films and ([B] + [P]) or [B]/[P].
On the whole, BPSG films have been shown to be
good dielectrics. Some specific data are given below.
The dielectric strength of BPSG films is in the
range 4.0–9.2 MV/cm. In particular, methods 1 and 2
yield films with 4.7–6.6 and 7–9 MV/cm, respectively.
With method 1, the leakage current at an electric
field of 1 MV/cm is about 5 × 10−7 and ~1 × 10–8 A/cm2
before and after annealing, respectively; the leakage
current decreasing with falling deposition temperature
[19]. With LPCVD using esters (method 3), the leakage
current at 0.5 MV/cm is about (4–8) × 10–9 and (4–13) ×
10–9 A/cm2 before and after annealing, respectively
[23, 52].
The electrical defect density, as measured by alu-
minum-capacitor techniques, is found to be 0.15 cm–2
(voltage 130 V, area 0.114 cm2) [38] or 0.3–0.6 cm–2
(voltage 25 V, area 0.092 cm2, limiting current over
500 nA) [19].
RUSSIAN MICROELECTRONICS
The dielectric constant at 1 MHz is in the range
3.8–4.5 [43], 3.88–4.11 [57], or 5.0–6.0 [19], depend-
ing on the deposition method.
With methods 1 and 3, the sheet charge density of
films with [B] = [P] = 4 wt % is (2–4) × 1011 [19] and
(5.3–5.7) × 1011 cm–2 [23, 52], respectively.
The net charge of BPSG films on monocrystalline
silicon substrates was measured by a noncontact, non-
destructive method known as surface photovoltage
[58, 59]. This consists in the laser illumination of a
film–substrate system with the result that the film sur-
face acquires a potential correlating with the net charge
of the film [60]. The method of surface photovoltage
made it possible to reveal differences in electrical prop-
erties between BPSG films deposited by method 3 and
subjected to thermal processing at different tempera-
tures and for different lengths of time. Furthermore, the
films displayed a highly nonuniform charge distribu-
tion over the surface, the substrates being 200 mm in
diameter. With method 4, no charge variations were
detected on films with similar composition. The differ-
ence in charge distribution was therefore related to
those in density and structure between the films fabri-
cated by the two methods.
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